clhynabee lu aba - vtechworks

,AN X-RAY STUDY OF THE BEHAVIOR OF

TITANIUM FILMS ON SILICON SUBSTRATES ,

by

Frank E.,Dietrichy;,

Thesis submitted to the Graduate Faculty of the

Virginia Polytechnic Institute and State University

in partial fulfillment of the requirements for the degree of

MASTER OF SCIENCE

in

Metallurgical Engineering

APPROVED:

x A: CLhynabee Lu Aba C. R. Houska, Chairman W. R. Hibbard

. _-4

J. T. P. Floridis L. Lytton”

June, 1977

Blacksburg, Virginia

TY) SSS

VASS \At7I

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ACKNOWLEDGMENTS

The author expresses his thanks to Dr. C. R. Houska who provided

the challenge and assistance required to complete this work. Thanks

also go to Drs. T. P. Floridis and J. L. Lytton for their interesting

and useful discussions.

Thanks are also due to Mr. Harry C. Dudley and Mr. Lawrence

McDonald, both technicians for the Department of Materials

Engineering. Appreciation is extended to Mrs. Teresa K. Belcher ©

for the typing of the manuscript and Mrs. Jeanne Warner for her

assistance. Thanks also go to Lawrence P. Johnson for his help in

computer graphics.

The author wishes to express his thanks to his family and

especially to Mr. James E. Kramer for his untiring encouragement

and financial assistance to both his daughter and son-in-law. Long

overdue thanks is offered to his wife, Robin, for her loving care

and encouragement.

The author is grateful to the National Science Foundation for

providing the funds that made this research possible.

Li

TABLE OF CONTENTS

ACKNOWLEDGMENTS . 6 6 we ee ee ee ee ee ee ee

LIST OF FIGURES. 2... ee ee ee ee ee iv

LIST OF TABLES... 1... ee ee ee eee ee ee VEE

I. INTRODUCTION. . 2. 2. 6 6 ew ew ew ew ew ww we we we ew ee eh el UL

II. REVIEW OF LITERATURE. . 2... 1 1 eee ee ee ee ee ee

III. THEORY. 2. ee ee ee ee 9

IV. EXPERIMENTAL PROCEDURES...) 1. ee eee eee ee ee 24

V. ANALYTICAL PROCEDURES . ~~... . ee ee ee ee ee ee 38

VI. RESULTS AND DISCUSSION... .....-----4-024. 43

REFERENCES. . ee ee eee ee ee eee ee 1168

APPENDIX Le ww ee eee ee ee eww LL

APPENDIX ID. we ee ee ee ee A LB

VITAL fc ee ee eee 193

ABSTRACT

iii

LIST OF FIGUR:S

Figure Page

1. Equilibrium phase diagram of the titaniun-silicon syst em e ° *. * ° e s * a . ct . a ° *. e e e e ° a . s * e e 6

2. Plot of linear expansion vs. temperature for the

components of a reacted thin film. ............ 10

3. Illustration of axis designation for a texture diffractometer . . . 1... 1 ee ew ew ew ww ew ew we ew we et 1

4, X-ray diffraction geometry ......... 4.4.44 .64. 14

5. High resolution Koy diffractomete« with line source. . .. 33

6. Schematic drawing of elimination 95f Ky, component. ... . 34 2

L. 7. Plot of heat treatment temperatu) 2 (°c) vs. (time)? to

fracture of cyclic anneals on thii films ......... 48

8. Scanning electron micrograph of titanium thick film

surface (2.2 um) after cyclic anr2al at 650 C, total

time of 2 hours. . . 1. 6 6 ee ee we et we tw ww ew ew 49


surface (2.2 um) after cyclic anreal at 650° C, total

time of 5 hours. . . 6. 1. 1. 1 6 we ew ee ww wee ew ee OD


surface (2.3 um) after total annealing time of 1 hour

at 625° CGC. ww ew we ww tet wt tt lt le le tle te lt lw ew OL

ll. Scanning electron micrograph of -:itanium thick film

surface (2.5 um) after cyclic anieal at 600 C, total time of 745 hours . . . 1 1 ee ew ee ee we ee ee ee ee «C2

12. Experimental intensity simulation for as-received

2. 2 pm titanium-silicon thin fila, 26 region from 35° to AS ee ee ee ee 60

13. Experimental intensity simulation for as-received 6

2.2 micron titanium thin film, 2¢ region from 70 to 80 . 61

14. Experimental intensity simulation for step. anneal for

2 hours at 350° C, 28 region from 35° to 45°... 2 wee 62

iv

Figure

15.

16.

17.

18.

19.

20.

21.

22.

23.

24.

25.

26.

27.

28.

29.

30.

Experimental intensity simulation for step two hours at 350° C, 26 region 72 to 73°

anneal for

Experimental intensity simulation from oreo anneal for

2 hours at 450°C, 20 region from 35° to 45

Experimental intensity simulation for 9 Step

2 hours at 450° C, 26 region 72° to 79°

Experimental intensity simulation for step)

2 hours at 500° C, 26 region from 35° to 45°

Experimental intensity simulation for step


Experimental intensity simulation for step.


Experimental intensity simulation For step

2 hours at 550 C, 29 region from 72° to 79°

Experimental intensity simulation for step


Experimental intensity simulation for step |






Experimental intensity simulation for step 2 hours at 600°C, 20 region from 71° to 79°.

Experimental intensity simulation for step. 2 hours at 625° C, 28 region from 35° to 46°

Experimental intensity simulation for SreP o®

2 hours at 625° C, 28 region from 59 to 63


2 hours at 625° C, 26 region from 70° to 83°,

Experimental intensity simulation for. sted


anneal for

anneal for

anneal for

anneal for

anneal for

anneal for

° . . e °

anneal for

anneal for

anneal for

anneal for

anneal for

anneal for

anneal for

* . . * e °

oanneal for

» a

Page

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

Figure

31.

32.

33.

34A.

34B.

35.

36.

37.

38.

39.

4Q.

41.

42.

43.

44.

Experimental intensity simulat:on for step, anneal for

2 hours at 650° C, 260 region from 60° to 63°... .

Experimental intensity simulation for step. anneal for 2 hours at 650° C, 28 region from 72° to 79°

Experimental intensity simulation for step anneal for


Optical interference techniques measured the elastic

bending of the silicon substrate taken at right angles

Optical interference technique; measured the elastic

bending of the silicon substrate taken at right angles

Optical interference techniques measured the elastic

bending of the silicon substrate cu’ to within 3. 5° of

the 111 planes ........4.+4.-.64+24484

Experimental intensity simulation for as-received,

2.3 pm titanium thin film, 26 regiou from 34° to 42°


2.3 um titanium thin film, 2@ region from 52° to 54

Experimental intensity simulation for as- -received,

2.3 pm titanium thin film, 20 regior from 62° to 64°


2.3 um titanium thin film, 29 region from 70° to 84°

Experimental intensity simulation for 15 minute anneal

at 625° C, 28 region 34° to 42° 7. ke ee ee


at 625° C, 20 region 75° to 79°


at 625° C, 20 region from 80° to 84°... 2.


at 625°C, 28 region from 34° to 42°


at 625° C, 28 region from 59° to 62°. .....2..

vi

Page

79

80

. 81

82

83

84

85

. 86

87

88

. 89

90

91

92

93

Figure

45.

46.

47.

48.

49,

50.

Sl.

52.

53.

54.

35.

56.

57.

58.


Page

at 625°C, 26 region from 70° to 83°. oe - 94

Illustration of cross-section of thin film structure

for as-received and 350 C step anneals for 2 hours . 95

illustration of cross-section of thin film structure

for 450 C step anneal for 2 hours. . . woe - 96

Illustration of cross=section of thin film structure

for 500 C anneal for 2 hours .... oe 97

Tilustration of cross-section of thin film structure for 550 C step anneal for 2 hours... - 98


for 575 C step anneal for 2 hours. . . 99


for 600 C step anneal for 2 hours. . . L00

Illustration of cross~section of thin film structure

for 625 C step anneal for 2 hours. . . -LO1


for 650 C step anneal for 2 hours. - 102

Plot of "G' factor vs. disilicide thickness; in final step anneal treatment at 650 C for 2 hours ..... .103

Plot of strain vs. temperature increment above

deposition temperature perpendicular to the crystal-

lographic planes in step annealed thin films... - 104

Experimental intensity simulation for step anneal at

350 C for 2 hours, to illustrate the location of mono-

Silicide in this film. .......... 2... .42.. . .105

Terminal selection panel on the PDP 8/e rack .... .173

PDP 8/e computer... 1 4. 1 ee ew ee ee ee ew ew ww We LT4

vil

Table

II.

Ill.

IV.

VI.

VII.

VIII.

IX.

XI.

XII.

XIII.

XIV.

XV.

LIST OF TABLES

Completed Reflections of TiSi, (C54).

Atomic Scattering Factors .

Reflections for TiSi. .... . . . s . °

Intensities for 20 Region, As Received 2.2 jm

Titanium Thin Film. .....

Intensities for 29 Region, Step

at 350°C.

Intensities

at 450°C.

Intensities

at 500 C. .

Intensities

at 550 Cc. .

Intensities

at 575 C.

Intensi' ies

at 600 (. .

Intensities

at 625 °C.

Intensities

at 650 C.

Intensities

Thin Film.

for

for

for

for

for

for

for

for

20 Region, Step

° *. ° . °

26 Region, Stef

. * ° e °

26 Region, Stef

* ° » e e °

26 Region, Step

26 Region, Ste;

26 Region, Step

26 Region, Stef

. * e

° e .

Anneal for 2

Anneal for 2

Anneal for 2

Anneal for 2

Anneal for 2

Anneal for 2

Anneal for 2

* e * . e

Anneal for 2

Hours

Hours

Hours

Hours

Hours

Hours

Hours

Hours

28 Region, as Feceived 2.3 pm Ti

°

Intensi:y for 26 Region, 15 Mirute Anneal at 625°C.

Intensities for 26 Region, 30 Minute Anneal at 625°C.

28 Positions for Experimental Intensity Simulations .

viii

- 112

120

. 122

. 124

127

130

133

. 136

. 140

144

149

152

154

157

Table

XVII.

XVIII.

Page

28 Positions for Experimental Intensity Simulations . . . 163

Thin Film Specimen 2.5 Micron of Titanium Cut Within 3.5° of the 111 Planes Annealed at Various Temperatures

for 2 Hours, Measured at Room Temperature ....... . 166

I. INTRODUCTIO.J

Preliminary investigations of titanium-silicon thick films are

incapable of presenting quantitative models describing their behavior

at intermediate temperatures. The silicides associated with diffused

-thin film structures have received limited attention thus necessitating

conclusive determinations of structure and lattice parameters. The

confusion in the literature on the reaction between titanium films

and silicon possibly stems from the acceptance of previous incomplete

and inaccurate studies of the bulk silicides. The characterization

of this transition metal system is the purpose of this study.

The nature of X-ray diffraction makes it a particularly attractive

tool for analyzing diffusion on the order of several microns in

specimens. Refinements in the analysis of diffraction data have made

it possible to investigate uniform and non-uniform strains, grain

size, stacking faults and other defects as well as texture and crystal

structure. Grain boundary diffusion and volume diffusion in films

can be studied quantitatively in detail with an X-ray technique.

The titanium-silicon thin film system has been mainly examined with

MeV He backscattering along with some supporting K-ray diffraction.

A detailed study on thick film specimens which are free of oxides

at the interface was carried out. Titanium films of approximately

two microns thick, a factor of ten thicker than in previous studies,

were deposited on 111 oriented silicon single crystals. An additional

complication evolved from the highly deformed nature of the deposited

metal films. The diffraction line broadening found with these films

is probably considerably greater than that of cold worked titanium

filings at room temperature. A computer simulation data analysis

technique was developed to evaluate the diffused structure of the

films..

The build-up of strain about the various interfaces and its affect

on the long term mechanical stability of the reacted film is a major

concern. Examination of both uniform and ncn-uniform strains resulting

from various heat treatments and substrate orientations supplied some

insight as to the origin and subsequent reduction of the mechanical

instability.

Lattice parameters and structure factor determinations of both

titanium monosilicide and disilicide eliminated a major problem for

identification of these phases with X-ray diffraction. A range of

compositions along with the identification of TisSi, as a high

temperature phase will modify the most recent phase diagram‘ (see

Figure 1). Results of the bulk titanium si icides represent

significant differences from those integrat:d intensities and lattice

parameters previously reported.

Finally, it should be noted that the d:terminations presented

in the following sections have not completely charécterized the

titanium-silicon system. A continuing effort in tle examination

of diffused films and bulk standards will eventually complete the

study.

IIT. REVIEW OF LITERATURE

‘In the past ten years, a renewed inter:st in the silicides of

titanium evolved from their importance in iutegrated circuits and

energy conversion devices. These applications impose an acceptatle

period of operation at a given temperature ind consequently encourage

the development of new techniques to measur: composition and structural

changes on a fine scale. The thin film rea: tion between silicon and

titanium may differ from the ordinary diffu.:ion process in bulk

samples at elevated temperatures. Baluffi ::nd Blakely‘) have

attempted to identify and describe a number of special characteristics -

for diffusion in thin films. Although prel minary work has been done

on this system, it is not as clearly unders ood as many conventional

engineering materials.

A technique using the energy spectrum of MeV backscattered He

ions provides sensitive measurements of relative atomic composition

as a function of depth. This method along with glancing X-ray

diffraction furnish specific pictures of the transformations in thin

films after thermal treatment. Although there is some disagreement

as to whether ion backscattering is nondestructive ‘7??? (since it may

create some defects which could influence the diffusion data) it is

at worst categorized as "nearly nondestructive" , The subsequent

information, which has been collected for the thick film reaction

between silicon and titanium (less than one nicron) has made use of

this technique.

Silicide formation is most commonly obtained through direct

reaction of a vapor deposited film on an oriented silicon substrate.

Typically one, and in a few cases two, silicide phase(s) are formed

3) in thin film structures after thermal treatment ‘ . The minimum

reaction temperature and the silicide phase(s) present in reacted thin

film structures are dependent upon the extent to which the native

(253). "The thickness of native oxide

(3)

silicon oxide film is present

layer is markedly different for different substrate orientations.

Film cracking and peeling aftcr thermal treatment, which is often

enhanced for thicknesses greater than a few thousand Angstroms, has

(3) also been correlated with these silicon oxide layers

(2) Mayer and Bower have reported that titaaium disilicide forms

at approximately one-half its absolute melting point (600°C) in thin

film structures where the substrates are oxide free. Prior to the

formation of TiSi Tu 6) »? has suggested that the lower free energy

monosilicide of titanium will form. In both the zirconium and

hafnium-silicon systems, these transition monosilicides have formed

(3) during thermal treatment » but no direct evidence was found for

1 a

the analogous titanium-silicon system. A relationship of (time)?

(3 os was found for the growth of titanium disilicide ), which is character~

istic of a diffusion dominated process. Silicon was identified as

(6) the diffusing species in the titanium-silicon system by the use

of implanted nobel gas markers.

(6) It has been postulated that since silicon is the diffusing

species, it will leave vacancies near the silicon-silicide interface.

If these vacancies coalesce to form voids, the silicide could fracture

(1) easily under an applied stress. Balluffi and Blakely~~ have reviewed

several explanations as to the origin of re!atively large biaxial

(7,8) stresses often present in thin films - Commonly found stresses

, 9 10 ~2(7,8,9) , of the magnitude 10° -10 dynes cm are likely to affect the

thin film diffusion process and the stabilicy of the conesive inter-

(10) face forces. Dearnaley and Hartley emphasized that several

intermediate phases formed in the diffusion zone are brittle and

easily susceptible to fracture. These effects are recognized in oxide

films but little attention has been given to thin metal film processes.

Direct information on crystal structure, grain size, internal

strains, and the texture in thin film structures has not been obtained

with ion backscattering. It should be pointed out that there is

disagreement among authors (11> 12) as to the structure of TiSi,.

(2) Titanium disilicide, identified by Mayer and Bower » was reported

to be of the orthorhombic C49 type. Preliminary work by Kato and

(13) Nakamura using X-ray diffraction has reported both the C49 and C54

orthorhombic structures in the same thin film of titanium and silicon.

(11), Cotter, Kohn and Potter have claimed that TiSi

(14)

9 is dimorphous

Another author has inferred that the C49 orthorhombic

disilicide is a ternary phase containing aiuminum.

(15) An examination of the phase diagram for the titanium-silicon

system (Figure 1) indicates that a number of intecmediate compounds

are observed under equilibrium. At the resorted reaction temperature

for thin films, approximately one-half the absolve melting point,

TEMP

ERAT

URE

°C

2200

T J t 1 ' qT | tT 1

B3h8 Ti,Si., i Si

; 2130 f3-4 | 920°

1800; TiSi, 4

TiSi oO ,

1665 1570° ,

' 3X 1500 ,

softy P1420 1420° 1400} £340° \ :

5% 13%! 1330° . \ |

1170° “| U7”

1000+ /

1.1% 860°

600 —l 4 L 1 1 _4 t

Ti 20 40 60 80 am.%

si—

Figure 1. Equilip riu

system 15),

lum phase diagram of the titanium-silicon Anea in dotted circle is incorrect.

the solubility of silicon in titanium is less than one percent. The

solubility of titanium in silicon is negligible. The crystal

structures for the Ti-Si system are: orthorhombic Tisi, with a C54

structure 12) | a = 8.236, b = 4.773 andc 8.523A; a C49

structure‘)? also orthorhombic, a = 3.62 + 0.01, b = 13.76 + 0.01

and c = 3.60 + 0.01; TiSi is also orthorhombic ‘1° a = 6.544,

b = 3.638, and c = 4.997; Ti,Si, is hexagonal of the D8, type with

a = 7.429 andc = 5.13924. 2”)

Reacted transition metal films yield silicides which range from

(18) nearly random to textured or epitaxial , and consequently some

preferred orientation or texture may be anticipated in any sample.

The subsequent study is an effort to exemplify the use of X-ray

diffraction as a technique which can better characterize both texture

and strain effects in thick films. Emphasis is placed upon the strains

which are present in the plane of the film and their effect upon the

stability of the reacted structure.

Summary

1. Existing studies have been of a preliminary nature using

nearly nondestructive techniques, mainly MeV backscattering

with some supporting X-ray diffraction.

2. There have been no studies which kave measured the effects

of either stress or texture on the diffusion process in thin

films.

3. Grain boundary diffusion and grain size have aot been

properly addressed in silicide formation.

The effects of epitaxial growth on the stability of the

diffused film have not been addressed but have been shown

. . . . (19) to be important in the Pd-Si system by Hutchins and Shepla

A detailed kinetics study on thin film specimens which are

free of oxides at the interface is still to be carried out.

Conclusive determinations of structure and lattice parameter

of both TiSi and TiSi, in bulk samples are absent. 2

III. THEORY

An X-Ray Diffraction Approach to a Kinetic Model

Introduction

X-ray diffraction provides non-destructive measurements of both

(20, 21,22) in films. volume diffusion and grain boundary diffusion

High diffusivity paths, such as grain boundaries and dislocations,

are known to be important at lower and intermediate temperatures

and are of significance in determining the behavior of material

systems.

(18) Random to textured or epitaxial silicides form in reacted

transition metal films. The problem of texture must be considered

if accurate measurements of the thickness of growing phases are to

be made. The diffraction equations should be sufficiently general

to treat phases with various degrees of preferred orientation.

Thick metal films are capable of withstanding a surprising amount

of mechanical deformation during cooling from elevated temperatures.

The deformation results from large differences in thermal expansions

of the individual materials (see Figure: 2). Strain data can be

measured in three ways: (a) X-ray linc shifts (uniform strain),

(b) line broadening (non-uniform straii), and ‘c) the elastic bending

of the substrate.

An X-ray diffraction approach is « escribed along with experi-

mental results to illustrate methods wi ich enatle the determination

of a kinetic model. Only after understanding the texture and strain

10

1.0 T ¥ } ’

TiSig —

0.8 |

&

et oO

” < O.6F oa Titanium a . Gs (// a-axis ) a 44 © . Y a Titanium

37 .0C(C«OOW4 LL (// c-axis )

rt ow E o & E

0.2 -

0.0 , 200 800 1000. 1200

Temperature (°K)

. . . 28 Figure 2. Plot of linear expansion vs. temperature ) for the

components of a-.reacted thin film.

il

developed in thick films, along with the identity of reactant products

either deposited at the grain boundaries or at the interface, will

this system be characterized.

X-Ray Diffraction Theory

The diffraction equations below are for a polycrystalline film

deposited on a silicon single crystal substrate. Polycrystailine

materials require texture information to obtain quantitative results.

The use of parafocusing geometry results in simultaneous measurements

of an orientation function and the reactant phase thickness. At later

stages of this development the diffraction equations will reflect the

experimental limitations observed in this study.

Two mutually perpendicular angles, x and © (Figure 3), allow

various sample orientations. Phi is perpendicular to the specimen

surface. The plane containing the incident and diffracted beam also

parallel to the specimen surface contains the x axis. Specimen size

limitations restrict examination to 60° in x and a full rotation in

d. Chi should be taken as 0° when the specimen surface is perpen-

dicular to the plane defined by the incident and diffracted beams.

The area of the specimen sampled by tie X-riy beam is given by

A, = A,/sin 8 cos x (1)

where A, = cross sectional area of the incident beam, and @ = angle

of incidence. Sampling depths«range from the specimen surface to a

depth at which the absorption from the material <ebove will reduce

the diffracted beam intensity to that of statistical background.

L2

Figure 3. Illustration of axis designation for a

texture diffractometer.

13

The maximum path length of the X-ray beam (Figure 4) 1-2-5 depends

on the linear absorption coefficient as well as on 6. As the

sampling plane with cross section A. is lowered parallel to the

surface and the interface, regions of composition "m" are examined.

The fraction of irradiated area with composition "m"’ intersected by

the sampling plane, at a depth "Y" is defined by the function HY).

For one dimensional volume diffusion, the sampling plane will pass

through regions of uniform composition, Hs = ] in the depth Ya to ae +

AY and He = 0 elsewhere. Irregular composition surfaces associated

with high diffusivity pzths may also intersect the sampling plane.

In either case the function H@) will be useful in subsequent

calculations, since X-ray intensity is proportional to the volume

of diffracting material of composition "m".

The total volume of material of composition "m'' is given by

W

Vy =A ‘/ 4 (y)dY (2) m @o mM

where w is the sample thickness. The form of equation (2) neglects

absorption of the incident and diffracted beams, i.e. the term

exp [-K u(¥)Y¥] (3)

where K_ = 2/sin @ cos x m m

must be included. The angle oF is the Bra :g angle for an element of

composition 'm" and p(Y) is the average linear absorption coefficient

for all material from the surface to a depth Y. Equations (2) and

(3) combine into a single expression defined as the effective volume

SIZE —_—____—__-»

SURFACE

INTERFACE

hNTene

Fiber Axis

——-A 6 ly

8m

1° { % —TH

aa v ae 7 x Z — 7

C f= — f- / " pa X 7

X 7 X Z

Je mee mes ee eee ee a ee 7 x ZL

w x 7

é , N TELE EEE

a

La \| samen \ / _f

PLANES 7

1. =

t | s a Catlin

Figure 4. X-ray diffraction geometry.

15

<Ve ms sO OOA, i H_(¥)exp[-K yu (¥)¥]d¥> (4)

The integral has been extended to = Since the integrand vanishes for

thick substrates. The orientation factor, 00> represents the ratio

of the actual pole density for a specific composition "m" to that of

the ideally random case. Rotational symmetry may be assumed for the

present application of diffused planar films deposited onto oriented

single crystals.

The diffracted intensity is proportional to the effective volume,

Vie? and is given by the following equatior

Pa ~ ten me” . (>)

where Ow the reflectivity per unit length, 72°2” .

rn 1+ cos26 cos”2a 2

Ge a7 OF, exp[-20, ] (6) vn sin 26 (1 + cos’ 2a)

The constant terms are:

I_ = intensity of incident beam, o .

re classic radius of the electron (= e”/me*)

A = X-ray waveleng <h.

Terms dependent upon the composition, 11, of the diffracting element:

Via = volume of unit cell,

N |

F = structure factor = £ f_ exp[?a(hu_ + kv + dw_] (6a) m 1 2 n n n

16

fo = atomic scattering factor, /

us Yn? = coordinates of the atoms in the unit cell

N = number of atoms per unit cell

exp[-2M_] = Debye-Waller factor,

oF = Bragg angle for diffracting composition

angle for the monochromator. a

Equation (4) may be written in terms of an average over a hemisphere

for a specific oF

A n/2 “9

= —?. f -K u(Y) <V nee sin a 5 0&0 tan x S H(t exp l K CY ]d¥dx (7)

a/2

with the J 00 sin x dx = 1 (7') oO

The integral can be carried out if the transformation products are

planar and of uniform ecmposition to a depth Y. The general case has

several planar phases b:tween the suxface and the diffracting phase.

The intensity for an intermediate phase of composition "m" is

A, w/2

Pr. Tal au : 0x) sin x [1 - exp(-K u Y)] x

exp (-K_u(Z)¥) Idx (8)

where Y = distance to the surface,

Y thickness of planar composition"m", and the average linear m

Nt

absorption coefficient is given by:

17

Y I ucyv)dy (9) Q

KL

u(y) =

The integrated intensity of a single uniform phase with a texture

represents the limiting case of equation (8):

A, n/2 = —_—— f ; Pa TQ, 2h ; 0% sin x)dy (10)

letting Y > O and va +o, The last integral is unity by (7') and the

effective volume expression reduces to

<V >= co (11)

which is the effective volume for a uniform phase.

Existing literature on silicide formation in thin films indicates

that the planar model is adequate. Equations (4), (7'), and (8) (or

simplifications) can be used to determine phase thickness, we and

the distribution function, 0 6X) - In the case of epitaxial phases,

(20,2122). In this methods are available to give similar information

case, X-ray rocking curves and integrated intensities supply the

distribution of subgrains and phase thickness respectively.

Experimental Limitations

The long term mechanical stability of the reacted thick film is

limited by the build-up of strain about the various interfaces.

X-ray data obtained by systematic isothermal anneals provide

diffraction lines which overlap and are considerably broader than

those obtained from cold worked metal filings. Chi rotation, carried

out with an Eulerian cradle, would result in a complex analysis of the

X-ray data. A simplification of the development presented above is

given in the following section.

The effective volume, equation (4), reduces to the following when

conventional reflection geometry is assumed

Ve. = A.8 i HY) exp[-K_u(Y)¥]d¥ (12)

where g = 00x) and chi is restricted to + 3.4°, The intensity for

an intermediate phase of composition '"m" is given by

rd I TQ A.8ft - exp (-Ku_Y_) :exp[-K u(Y)Y] (13)

where Y = distance to the surface

Y thickness of planar composition "m'" and the average linear Pp Pp g m

absorption coefficient is given by equation (9). The orientation

factor, g (eqn (12)), designates the volume fraction of grains that

have {hk&} plane normals lying parallel to the fiber axis (see

Figure 4).

Bulk standards allow the X-ray data to be reduced to the

effective volume term of the various silicides (and pure materials)

given by equation (11). From an ideal powder standard of a, the

intensity is

A e)

P, = 1,9, a (14)

19

where "g"' = 1, a randomly oriented material. For a given hk&

reflection the ratio of a standard powder to that of the general case

of a thick film structure yields the following intensity relationship:

<P ,> QQ, #

a O a _—

P =o => X,8ll - exp(-K <u, >¥, Jexp[-K u@)¥] (15) a a a

. (25) Harris has shown that the values of Syke? averaged over all

orientations, is equal to unity:

zg hke _ TO ee)

where N is the total number of reflections. If only a few reflections

are available, equation (16) may no longer be valid.

Equation (15) or a modification of it can be used to consider

a homogeneous dispersion of "o" in a thick film or a columnar reaction

product at the grain boundaries. In this case the grain size is

assumed to be much smaller than 1/ny- Through the use of the

preceding equations, a kin2tic model for silicide formation in the

titanium-silicon system will be developed.

Simulation of X-ray Patterns

The complexity of X-ray diffraction patterns obtained from highly

deformed materials necessitate the use of computer simulation in

their analysis. Symmetrical diffraction peaks are often represented

by simple mathematical functions. Gaussian or Cauchy distributions

20

are often inadequate in representing the X-ray intensity distribution

near the peak position and at its extremities. A Pearson Type VI

(26) distribution can be varied from the Gaussian to a Cauchy by

appropriate selection of a parameter in the function. A modified

Lorentzian and other forms of this function can be used to effectively

approximate many X-ray diffraction peaks (27) |

The Pearson distribution has the following form:

y(X) = Yo[L + (K - %)°/ (ma), (17)

and the maximum value, Yo? at X. The integration of Pearson

distribution yields

Pm = 3) y (18) l= i Yf1+ &@ ~ X)7/ (ma) J Max = vim a T (m) oO

where I is equal to the total integrated intensity. This integration

contains the distribution maximum and solving

_ I tT (m)

Yo vim a F(m - 4) (19)

where "a'’ is related to the full width at the 1/pt® maximum.

W(Y/P) = 2avm(pl/™ - 1) (20)

The limiting forms of the Pearson distribution are

-1 Cauchy, m= 1, Y(X) =Y [1+ & - %)*/a-] (21)

YG = I/(at)

and Gaussian, m= ~, Y(X) = Y exp l[-(x ~ X)*/a7] (22)

Y, = I/(ayn).

The form of the Gaussian is derived by expanding the function as a

binomial and considering the limiting form of the general term of

the series. This study will make use of intermediate forms of the

Pearson Type VII distribution in simulating X-ray diffraction patterns.

Diffuse Intensity

The contributions to diffuse intensity from thermal vibrations,

Compton modified, and X-ray fluorescence is part of the measured

integrated intensity which is not included in equation (6). Thermal

vibrations reduce the intensity of crystalline reflections (Debye-

Waller factor, exp[-2M]) and also produce a diffuse intensity (TDS).

The-incident radiation will fluoresce the absorbing element, given the

required absorption edge and produce ¢n additional contribution to

the diffuse intensity. Compton modified scattering is present in any

diffraction pattern. Significant infccmation on the reacted

Specimen is available from these intensities.

The diffuse intensity from Comptcn modified and TDS can be

approximated by the form

2 D _ _ sin 6

Tcomp.,tos ~ *, 1 ~ exPI-K, 2 )) (23)

which gradually increases with 28. This is a convenient form for

22

fitting the experimental data, and both constants can be related to

theory at a later time if needed.

The X-ray fluorescence from titanium by the incident Cuky,

radiation takes the form

T (CuK, ) = KG - exp[-K,/sin 6]) (24)

Wi where K! > = Ing, (Ca) + Mpg HIT

Hp; (Cu) linear absorption coefficient of titanium with Cu

radiation

Ups gy (Cu) = linear absorption coefficient of silicide with Cu

x

radiation

Hp, (TL) = linear absorption coefficient of titanium with Ti

radiation

Uns ge (Ti) = linear absorption coefficient of silicide with Ti

° radiation

where Ung = FS? + “risa”

T = thickness of titanium-silicide films

X = Thickness of titanium

and Ki = I, C Afi (Cu) + Mpg (TL) I (24a)

I= intensity of incident beam

A, = cross sectional area of the incident beam

C = intensity of TiK /intensity of CuK = efficiency constant

which increases with decreasing. 26.

23

The effective volume of titanium after each diffusion treatment can

be cross-checked by the use of this flvorescence, which is independent

of orientation. The application of these two forms of diffuse

intensity will be described in detail in the Analytical Procedures

(Section IV).

IV. EXPERIMENTAL PROCEDURES

An examination of both thick films and bulk powder standards were

necessary to complete this study. The existing ASTM powder dif-

fraction card files for TiSi and TiSi, were discovered to be incom-

plete or inaccurate, and standards had to be prepared. These silicide

standards along with a Ti powder sample supplied the fundamental

information essential to pursue tre development of a kinetic model

of silicide formation in titanium-silicon thick films.

This chapter describes the procedures employed in the preparation

and reaction of both thick films and bulk powder standards. Certain

preliminary results from the preparatory stage of the powder standards

are also presented. A detailed description of the experimental

equipment is given for completeness.

A. Thick Film Preparation

This is an important stage of the research because one of the

purposes of this study is to obtain a thin film structure free of the

native silicon oxide layer. In order to clean this interface, the

silicon substrates were first placed in acetone in an ultrasonic

cleaner for twenty minutes. The samples were then sputter etched in

the same chamber where the metal films were later deposited. This

procedure did not allow th: Si to be exposed to oxygen prior to Ti

deposition. The etching ws done at 0.8 kV, 60 watts for 30 minutes.

The samples were subsequently heated to 340 and 360°C*, and the

Oo, . . . *Samples (b) were heated tc 275 C in order to examine the effects this

different substrate temperature would have on the fracture process.

24

25

titanium was then deposited at 2.1 kV and 300 watts. The sputtering

pressure of argon was 5 microns. The purity of the Ti target was

99.9%. Auger spectroscopy was used to determine the amount of sputter

etching required to remove the native oxide film on the silicon

substrate. Specimens were prepared at the Oak Ridge National

Laboratory by the Isotope Research Materials Laboratory.

Three different sets of thin film samples were received from the

Oak Ridge National Laboratory at different stages of the study:

1. Ti-Si specimens with a uniform deposit of 2.3 microns of

Ti within 0.95 to 1.00 of the theoretical density. The

substrates were cut to within 2.5° of the lll planes and

measured 0.5 x 0.5 x 0.01". |

2. Ti-Si specimens with a uniform deposit of 2.5 microns of Ti

within 0.95 to 1.00 of the theoretical density. The sub-

strates were cut to within 3.5° of the 111 planes and

measured 0.7 x 0.7 x 0.02".

3. Ti-Si specimens with a uniform deposit of 2.2 microns of Ti

within 0.95 to 1.00 of the theoretical density. The sub-

strates were cut to within 0.5° of the 111 planes and measured

to 0.875" in diameter, thickness of 0.013". These substrates

were purchased from Pensilco in Bradford, Pennsylvania with

a dislocation density of less than 500 em? resistivity, 1 ohm-

cm, and polished on both sides.

Samples for cyclic annealing studies measuring 0.1 x 0.1" were

cut from the as-received sampled using an ultrasonic milling machine.

26

The specimens were sandwiched between two glass slides using pyseal

cement. A 345 mesh boron carbide abrasive was used for cutting. All

samples were cleaned in hot (50°C) chloroform which was found to be

the solvent inert to both titanium and silicon, yet it readily removes

pyseal cement.

B. Bulk Standards Preparation

High purity silicon and titanium hydride powders, supplied by

(30) Ventron Corporation's Alpha Products » were used in preparing

the samples. Emission spectroscopy suppl:.ed by the manufacturer found

the silicon powder to be highly pure (iron the gieatest at 500 ppm).

Wet chemical analysis of the hydride found 94.5 4 O.1 weight percent

titanium, and from hydrogen evolution, 4 + (0.1-(.3) weight percent

hydrogen. All powders were mixed in methanol anc evacuated in a vacuum

desicator (1077 torr) and allowed to dry.

Titanium and silicon were mixed in the exact stoichiometric

ratio of:

18.8206 grams Til,

21.1794 grams Silicon

to prepare a 40 gram sample. The mixed powder was placed in a 3-inch

long, high alumina boat, and subsequently evacuated to i0°° torr in

an ion sorption vacuum system (see annealing furnaces, Section IV).

A total reaction time of 279 hours of annezling ensured complete

reaction of the sample in five steps at 1000°C. The first anneal

was 111 hours, of which 5 hours at 107" torr was due to hydrogen

. 3 ~6 . evolution. All subsequent anneals were at 10 torr during the

27

reaction. The weight loss could be attributed entirely to hydrogen

evolution in the initial anneal.

After each anneal (111, 24, 48, 48, 48 hours) the samples were

removed from the furnace and reduced to less than 37 um (-400 mesh)

particle size with a steel impact mortar. X-ray patterns were taken

without the use of a binder, and throughout the anneals the diffraction

lines remained sharp and no shifts were observed. Full reaction was

found after the fourth anneal with no evidence of residual titanium

or silicon. A fifth anneal was carried out to assure completeness

of the reaction. All X-ray patterns were made using a graphite

diffracted beam monochromator. This allowed very weak peaks to be

observable.

Titanium and silicon were mixed in the stoichiometric ratio of:

25.5973 grams of Til,

14.4027 grams of Silicon

for preparation of a 40 gram sample. All preliminary preparation

methods were identical to those employed wit the disilicide.

A total reaction time of 528 hours at 100°C in 11 steps assured

complete reaction of the standard. A111 anneals were 48 hours in

length of which 7 hours of the initial anneal was at 107 torr.

Weight loss again could be attributed entirely to hydrogen evolution

during the initial anneal. All sequential anneals were at 10°° torr

as in the disilicide treatment.

The X-ray diffraction patterns obtained with the same conditions

as before contained peak position shifts. Examination of the final.

sample found Ti,Si., and TiSi in the completely reacted state. A

10 atomic percent deficiency in silicon was determined and a corres-

ponding sample prepared.

All conditions remained the same as those of the previous samples

except the reaction temperature was increased to 1050°C. Seven treat-

ments of 48 hours in length produced a sample of only monosilicide.

The X-ray diffraction lines remained sharp and shifted to lower 26

positions during the treatment.

Each silicice powder of less than 400 mesh was filled into the

cavity of an aluminum sample holder after the final anneal. Acetone

and Duco cement (10 parts to 1) was used as a binder after the powder

was settled with acetone. This produced a sample with limited

surface roughness.

C. Annealing Procedure

Thin film anc. bulk sample heat treatments were carried out in

oil free, high vacuum furnaces which incorporate sorp*ion and ion

(20 liter/sec) pumping. Using both control and specinen thermocouples,

temperature measurements were within + 2°C. {interlocks in both

furnaces did not permit operation unless a vacuum of 107" torr or

better was maintained. Both furnaces and a general procedure is

described in the following section.

1. Bulk Standard Treatments

Powder samples were reacted at 1000 or 1050°C in a horizontal

tube furnace positioned around a quartz furnace tube which contained

29

the powders under constant vacuum. A West furnace controller provided

many different constant rise and fall rates, ranging from 20°F/hr to

300°F/min (0.001 to 1.0). Temperature was measured on a Brown Elec-—

tronic recorder with a chromel-alumel thermocouple which was in

contact with an alumina boat containing the powders. The furnace

control thermocouple was platinum-10% rhodium. A three-inch constant

temperature zone was measured at 1000° or 1050°C which was the reaction

temperature for all powder samples. Prior to heat treatments of all

powders, each alumina boat was air-baked at 1000°C for 8 hours in an

alundum tube inserted in the furnace.

A fused quartz, 3/4 inch I.D., tube was thoroughly cleaned in

acetone and methyl alcohol prior to any heat treatments. The alumina

boat located in the end of the tube was sealed to the vacuum system

by tightening two flanges against a copper gasket. The furnace was

positioned around the glass tube so that the constant temperature

zone enclosed the entire specimen.

If the following recommended start-up procedures are employed,

the inefficient pumping of samples to reaction vacuums will be

eliminated.

The ion pump is isolated from the remainder of the system during

an exposure to atmosphere. Dry nitrogen is bled to eliminate the

vacuum and a constant purge is continued during exposure to increase

pumping efficiency. A roughing vacuum is produced by filling the

sorption pump with liquid nitrogen. After a»proximately 15 minutes

the valve between the ion pump and the remai ider of the system may

be opened after valving off the sorption pum>. The vacuum should

stabilize at 5 x 10° torr and be allowed sufficient time to pump

well below this level.

The initial anneal produces a large amount of hydrogen at the

reaction temperature and is easily handled by the sorption pump.

During this anneal it is necessary to supply liquid nitrogen to the

sorption pump so that the roughing vacuum is not lost. This is

necessary for 5 to 7 hours at which time the ion pump may be bled

into the system. All subsequent anneals were done at 10° torr at

the ion pump. The rise rate of the furnace was set at 200°F per hour.

At the end of each anneal the samples were allowed to air cool by

retracting the furnace.

2. Thick Film Treatments

Thick film specimens were enclosed in a one-inch I.D. fused

quartz tube and evacuated to 5 x 10> torr. The vacuum was produced

with the same procedure described in the previous section. The

specimens were suspended in the tube on a horizontal high alumina

platform which eliminated contact of the specimen with the quartz.

A water cooled, open coil furnace was positioned around the sample

tube to produce a 3/4 inch constant temperature zone at 650°C (the

maximum heat treatment temperature).

Heat treatments of all thin films were carried out with the

"Thermac'' controller in the remote option. This option follows a

predetermined time-temperature profile ruled on a totating drum.

The limiter and gain controls were adjusted such that there was a

maximum of 2°¢ deviation between the chromel-alumel specimen and

command thermocouples. Limiter control enables the maximum voltage

applied to the heating coil to be any desired fraction of the full

line voltage. The width of the proportional band is dependent on the

gain setting; increasing the gain will narrow the proportional band.

For optimum control, the gain was 8 with the Limiter set on 4.

Cycled specimens (see Section VI and Figures 9-12) were heat-

treated with 50°C per minute heating and cooling rates at temperature

times of 5, 10, and 15 minutes. All stepped and isothermal anneals

had heating and cooling rates of 100°¢ per mi.iute.

D. X-Ray Measurements

The two X-ray diffractometers used to collect all data on bulk

and thin film specimens will be briefly described in this section.

Distinct advantages obtained through the use of this equipment are

emphasized.

1. Powder Diffractometer

(32) A Siemens diffractometer, allowing the specimen to be

rotated about the % axis (see Figure 3} independently of the detector

carriage, collected all data on the powder standards. The diffracto-

meter was used with a one-half degree cntrance, 0.2 mm receiver slit,

and a Soller slit in the incident beam. The data was collected with

a scintillation counter, a pulse height analyzer, and an E&S Industries

diffracted beam graphite monochromator. All final runs were made at

32

1/8° per minute. A silicon powder* standard was used to provide a

small correction to the bulk sample line positions. Integrated inten-

sities were measured using a planimeter after subtracting background.

The peak to background ratio was considerably improved with the

use of a diffracted beam sraphite monochromator. This diffractometer

set-up allowed relatively low intensity line measurements.

2. Single Crystal Diffractometer

The X-ray unit used to collect all data on the diffused thin

(32) films was basically a modified Siemens diffractometer, equipped

so that the Kyo component is eliminated. The instrument halfwidths

for a line source are 0.037° and 0.081° at 29 =~ 40° and 95°

respectively, which is only a factor of two _arger chan the natural

half-width due to the spectral distribution of the Ka, line using

Cu radiation.

The Kao component of the radiation from the hi:,h voltage fine

focus Cu tube was removed with an incident beam Jagodzinski singly

bent quartz crystal monochromator (see Figures 5 and 6). The total

elimination of the Kao component would result in an asymmetry of the

instrumental function. A ratio of 1:200 between Kay and Kay intensities

provided an insignificant contribution of K,, without causing excessive 2

high angle asymmetries. The monochromator was adjusted at this position

and remained there during the completion of the expcriments.

The data was collected with a one-half degree entrance slit,

0.05 degree receiver slit, a scintillation counter and pulse height

*Supplied by National Bureau of Standards.

BANOS

BUTT UFIM

ABJOWOROeATFIP

Toy uoTINTOSeI

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YOLYWOYHIONOW

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wwe

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JONVYLNE YOLYWOYHIONOW

SIX

Ss »

“WS wu}

ONINSdO JO

LHOISH --\

SNe

LINS VVOILYBA

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VY 3ygnodls

i /

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WLI

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\

s

YaLNNOD /

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NOLLYTULNIOS \

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LOds \I

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YOLVWOYHDONOW

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34

Ka, REFLECTED BY

MONOCHROMATOR CRYSTAL

_ ENTRANCE SLIT (0.5° DIVERGENCE)

Ka, REFLECTED BY Se VERTICAL ENTRA MONOCHROMATOR \ . SLIT— HEIGHT OF CRYSTAL aN OPENING 2mm

_

Figure 6. Schematic drawing of elimination of Koo

component (Section B).

analyzer. The arrangement provided high resolution and refined line

shape making it well suited for defect studies.

Use of the Diffractometer: The high voltage generator was warmed

up at the operating voltage for several hours prior to data collection.

The pure silicon 26 positions were found to be in constant error over

the 26 region (30° to 150°) and corresponding corrections were made

to the experimental line positions. The detector panel settings were:

Detector Voltage: 1200

Pulse Height Analyzer: 2.0 (base and window)

Linear Amplifier: 4 x 64

on both diffractometers

3. Thin Film Thickness Measurements

The weight gain measurement supplied by Oak Ridge Laboratory

was varified using an X-ray diffraction method. Using the integrated

intensity of one or more orders of the substrate reflections, the

thickness can be calculated as follows:

gn (I/To)

. Ung (25)

t = film thickness

I = intensity measured in the plated condition

1, = intensity in the unplated condit’ on

Weg = absorption coefficient of film material

Ko= 2

sin Oo.

Gay on

The silicon single crystal substrate first order reflection will be

decreased by extinction. The use of the third order reflection will

minimize this effect and yield reliable thickness measurements.

4. Locating the Specimen

The mounting of thick film specimens in vaseline eliminated

additional contributions to the large amount of strain present in the

titanium. Destruction of the sample was inevitable if conventional

backings were used (i.e. mounting clay), resulting in a local fracture

of the titanium from the substrate. The sample was positioned by the

weight of a glass slide placed on the sanple which caused the vaseline

to creep. This located the sample surface parallel to the face of the

X-ray specimen holder.

The thick films were cleaned of vaseline in ios-octane after each

X-ray examination. Prior to heat treatment, all specimens were cleaned

in acetone to remove all traces of the iso-octane and then rinsed in

methanol.

E. Optical Interference Techniques

The elastic bending of thick film specimens has bcen measured using

an optical interference (Newton rings) technique. St-ains in the

plane of the metallic film distort the substrate into a saucer-like

shape, thus presenting difficulties in mounting the specimens (see

previous section). Information on the deflection of the specimen

resulting from stepped annealing upwards from the depcsition tempera-

ture will compliment the strain measurements obtained with X-rays.

A monochromatic mercury (5461 R) light along with an optical

flat were used to produce a pattern of contours for the film surface.

The factors that determine the nature of the interference are

differences in optical path length and phase changes on reflection.

Assuming normal incidence, the respective minimum and maximum inten-

sities are

2d = md (26a)

2d = (m¥s)A (26b)

where A = wavelength

m= 0,1,2,...

d = deflection from one rin‘, to the next.

Perfect flatness will form a pattern of uniform brightness. Each

fringe represents a charge in height of 18 millionths of an inch.

' The surface of the specimens were wiped clean and the optical

flat placed in contact with the metallic side of the thin film. It

is essential at all times to have the flat level with the surface.

The monochromatic light, at normal incidence, illuminated the surface

so that a reflection of it could be scen in the sample. The pattern

was viewed from an angle of 30° to the specinen normal through a

macroscope (5X). The photographs takcn of each fringe pattern were

enlarged to 8" x 10", and the distance between fringes was measured.

V. ANALYTICAL PROCEDURE

Calculations of the structure factors and relative intensities

for various crystalline reflections of a material are dependent upon

the atomic positions of the atoms in the unit cell. Substances of

the orthorhombic crystal structure yield X-ray patterns containing a

larger number of reflections than those of a cubic material and

accordingly less non-zero structure factors. The diffracted intensity

pattern for a structure composed of several phases will consist of

the individual intensities from each sei of crystalline planes parallel

to the surface. The difficulty in dete mining the individual contri-

butions from each phase to the total di fracted intensity is magnified

if uniform and non-uniform strain along with composition variations

are present in the material.

The computer analysis of both comp ex diffraction patterns and

the general forms for the structure fac: 2rs will be discussed in the

following section. The simulation of t .e entire diffraction pattern

determines the effective volume of each phase present in the reacted

structure. This is possible only after having determined the

experimental structure factors for the constituents.

Silicide Standards

The calculated relative integrated intensity for a powder can be

expressed by a combination of equations 5, 6, and 11. The diffracted

relative intensity, neglecting a thermal correction:

38

39

1+ cos-20 cos 2a 2

Tel ~ 2 PF, [Tax sin 26(1 + cos’ 2a)

a = 13.3°

can be calculated by the computer program listed in Appendix II.

Atomic scattering factors for titanium and silicon are presented

in Table II.

In general, F. is a complex number, and it expresses both the

amplitude and phase of the resultant scattered wave. The structure

can be expressed as:

Py = f [cos 20 (hu, + kv + gw) + i sin 2 (hu. + kv, + ww)

(28)

where fA = the atomic scattering factor.

The diffracted intensity is proportional to FI? which is obtained

by multiplying the expression above by its complex conjugate.

| If the space group and structure are known for a material, the u_>

va W, can be introduced into equation 28) and the structure factor

can be calculated for each crystalline reflection. Experimental

structure factors and those determined from equation 28 can confirm

the positions of each atom in the lattice (us v5 and wi) by the

following relationship:

rl|F | - |FI| R = ——?—__+_ (29)

z|F | oO

40

observed structure factors ll where F Oo

F e

calculated structure factors (see Eq. 6a)

when R is called the residual for a set of structure-factor magnitudes.

In principle, R < .50 suggests a correct structure, although a con-

siderably smaller R is necessary to lend credibility to the proposed

structure.

Lattice parameters are determined from agreement of the high

angle lines and a deviation of no more than 0.02° of those at low

angles. The initial approximation of each parameter is obtained from

hk& planes of the form; two indices zero and the other having a large

value, along with substantial line intensity. An iterative computer

program has been written which gives four decimal place accuracy in

each lattice parameter.

Thin Film Diffraction Pattern Simulation

An X-ray intensity simulation prog:-am was used to calculate the

total diffracted intensity from a diffused thick film structure.

Contributions from each reflection of a phase located as a dispersion

or a film were summed to represent the iotal measured X-ray intensity.

The diffuse intensity was considered as a combination of temperature

diffuse, Compton modified and X-ray flucrescence scattering. A

Pearson type VII distribution approximated the symmetrical diffraction

peaks, since the asymmetry of instrumental function can be neglected

due to the large line broadening found in all crystalline reflections.

41

Detail about a simulated diffraction peak is obtained by solving

equation (17), which determines a 26 position given an intensity:

2 Y¥(x) vima P (ins) ji/m ~ 1) 20 + ([ma I, Gn) 28 lt C17")

20 uN the peak position

where Y(x) is the measured intensity at any 29 position. The intensity,

Ty is related to that of the powder standards by the following:

ri ] I -_ a , _ 1 a ~ Ig¢q & ¥ 14 - exp(-K <u?) lexpl-K <u (Y)°¥] (15')

q K 2/sin 8 ™

for the general case.

The full halfwidth, By and full quarter width, By can determine

the "m'' of the Pearson function for a peak having a shape intermediate

between a Cauchy and Gaussian distribution by:

m= kn 2 , (30)

B - 1)

L

4 ng

and "a" is related by equation (20). Uniform strain is treated simply

by the increasing or decreasing X in equation (17').

The form for Compton modified and TDS scattering (equation 23)

is evaluated by fixed point iteration at two high angle points. Using

equation (24), the fluorescence from titanium is fit to two low angle

. . . . . - os (38) . points and substituting the mass absorption coefficients is

expressed by:

42

I= K,Q - exp[.1391T/sin 6]) (31)

I CA K =—-0 _

1 1391.06

where T is the thickness of the titanium film in microns. The two

diffuse intensity expressions are summed to represent the background

present in the recorded diffraction pattern.

The criterion imposed upon the simulations are those of con-

servation of material and that "g'' will sum to unity. Each

diffraction region of interest is fit with the diffuse intensity

from the predetermined functions to which is added the contributions

of each diffracting phase. Reflections of the diffracting phase are

considered initially random in orientation (g=1). Uniform and non-

uniform strain along with a preferred orientation are introduced as

the simulation progresses. As a planar reactant product grows, a

linear variation of "g"' from the substrate interface to the metallic

film is introduced. The simulation of the entire diffraction pattern

provides a model for the amount, distribution, and structural

perfection of the reacted sample.

A comparison of the experimental data, introduced as points, and

the simulated X-ray regions are viewed on a Tektronix graphics terminal

during the refinement procedure. An area difference routine of the

simulated and experimental intensities increase the ease at which an

operator can converge upon a solution. The computer program along with

details of operation will be presented in a College of Engineering

technical report.

VI. RESULTS AND DISCUSSION

Results of isothermal, cyclic, and step annealed titanium-silicon

thick films will be presented in this chapter. Silicide powder results

represent the fundamental link in the analysis of the reacted thick

film structure. Thick film results are related to the bulk standard

kinetics observed and the appropriate analogies will be made. All

computer simulated experimental data is included to emphasize its

central role in the present analysis.

Silicide Powder Results

Titanium disilicide was confirmed to be face-centered, C54

orthorhombic, a space group of Ds = rada 632) | The atomic positions

are:

8 Ti in 8a: (000, *50, 30's, 0's's) + 000, eax

16 Si in l6e: (000,!:0,%0%,0%!s) + x00,x00, (etx), Ce-x) des x=1/3

The structure factors take the following forms for various hk&

combinations:

2 _ _ . _ 0 F 32(fa4 fo4) ; h 3° + 2, k and & are odd

Fo = 32(£..42F..)°: h = 3", k and & are odd Ti “Si? | °

2 2 n FO = 64(£,,-f55) ; h = 2°, k and & are even

2 2. _ 3 FU = 64(£,,,+2f, 5) ; h =n --n, k and 2 are even

RF = 0; h, k and & are mixed

where n = 1,2,3,...

The atomic scattering factors required in these forms were obtained

from the "International Tables for X-Ray Crystallography" °” , The

43

44

correctness of the structure was determined from equation (29) (see

Section V). When titanium and silicon are considered in the neutral

state, "R'' was found to be 0.09. With silicon in the *4 valance state

and titanium in the neutral state, "R'" is 0.07, and the corresponding

integrated intensities are listed in Table I.

The peak to background ratio was considerably improved with the

use of a diffracted beam graphite monochromater. This diffraction

set-up allowed relatively lov. intensity line measurements. Results

of the bulk titanium disilicide represent significant differences

from those integrated intensities and lattice parameters previously

reported (12233) | Our study found a unit cell intermediate in size

which may indicate that contaminates were present in previous samples

because of the less perfect annealing conditions. The unit cell

dimensions of TiSi. are:

2

Laves & Duffin, Parthe Present

Wallbaum (12) & Norton (33) Study _

a (2) 8.236 8.27, 8.2668

b, @) 4.773 4.81, 4.7987

c (8) 8.523 8.56, 8.5503

The initial anneal produced a powder which consisted of mono-

silicide and silicon. This indicates that the lower free energy

monosilicide of titanium forms prior to the formation of disilicide

in bulk samples. X-ray patterns taken after each reaction displayed

the absence of any significant solid solubility of either constituent

45

in the disilicide, since no line broadening or line shifts were

observed.

(16) found to be pt® space Titanium monosilicide was previously oH

group, orthorhombic structure based on powder photographs. A study

(36) L by Ageev and Samsonov reported a Coy space group. Photographic

work, confirming the compound stoichiometric composition (36.95% by

weight Si = 50 atomic 4) and established that titanium and silicon

are insoluble in this coipound. The lattice pirameters of the

orthorhombic cell were:

Brukel, Nowotny, Schob Ageev and

and Benesovsky ) Samsonov (36

a, (R) 6.54. 3.61,

b (A) 3.63, 4.96,

ec. (A) 4.99, 6.47,

6. space group were: The atomic positions for the Dow

+ (X,%, Z5 (4-X), 3/4, (1/2 + Z)

UW Hl 0.127 where Ti: X 5 0.179, 2

Si: X= 0.0355 Z= 0.61,

and for a Co Space group:

Ti (000, %s*s, 00's, 1550)

Si (0.412%, 40.588, 0.350’, 0.350 3/4)

*The parameter Z is given, but a diagram makes it clear that it is

incorrect.

£6

(16) The monosilicide sample of Burkle was sintered at 1000°C in

an inert atmosphere from titanium hydride and silicon powders. Ageev

(36) and Samsonov used iodide derived titanium (99.7%) and silicon

(99.7%) synthesized by sintering the powders in an electric arc

furnace with a copper bottom and tungsten electrode with no protective

atmosphere specified. The above information is presented to evaluate

the validity of the proposed structure for titanium monosilicide by

these authors.

Titanium and silicon reacted at 1000°C in their corresponding

stoichiometric ratio produced a two phase equilibrium bulk sample.

(37) - The presence of Ti and TiSi in this sample identified Ti Si Si 5 3 5 4

as a high temperature compound and a modification of the equilibrium

phase diagram (see Figure 1) is warrented. The low temperature

existence of TiSi at its stoichiometric composition was found not

to exist but instead, one ten atomic percent richer in silicon.

The lattice parameters for both compositions are:

TiSi Ti, Sigg

a. (R) 6.5291 6.5358

bd, (A) 3.3643 3.6363

ec (R) 4.9915 4.9969 0

and the respective integrated intensities are presented in Table

III (a) and (b). Table III (c) displays a comparison of the Burkle (1°)

16 experimental intensities to those calculated for the reported Day

space group. The residual, "R", is equal to 0.26.

47

Previous authors have not identified a range of solubilities for

TiSi as in this study. A systematic shift of the crystalline

reflections to lower 26 positions in the X-ray patterns taken after

each anneal identified this solubility. The volume of the

orthorhombic cell for Ti is considerably larger than the 40°*60 stoichiometric composition, thus indicating that silicon will occupy

additional positions in the cell. An intensity calculation introducing

titanium vacancies into the cell did not correspond to those measured

experimentally. A structure identification of the monosilicide

standard is unnecessary for the completion o” the thick film study

. Since experimental structure factors can be ‘ised.

Cyclic Heat Treatments

Large differences in thermal expansions (see Figure 2) between

the silicon and titanium-silicides, and not a thermal fatigue process,

were responsible for the mechanical instability of the thick films.

Three separate times, 5, 10, and 15 minutes, at temperature were

examined over a temperature range of 550 to 650°C (see Figure 7).

Identical samples were cycled until fracture at a given temperature

for different lengths of time at temperature. The results of these

tests at 650, 625, and 600°C showed the fracture time to be independent

of the total number of cycles in all samples (see Figure 7).

Samples cut to within a half-degree of the 111 planes exhibited

a gradual fracture process (see Figures 8 and 9) initiating at the

outer perimeter of the specimen. This fracture characteristic was also

found in the larger samples diffused in step heat treatments described

48

703. 00 | FF ' ,

yoy ae eee eM cul 4 660. 00 oe va to 0.5

™~ ceo Sumy cul + ONG LO Lo 2.5°

AA NN +

- a a“ Ty 620). 00 me NA 5 um,

TS NOt Lo 3.508 aa we or SN +

.. ——_

NN SS

‘S90. 00 NS NS

NO

540.00 + T

T tT

500, 00 -——+ he —+

co L. 00 2. OO 3.00 4.00 5 00

6 TIME

Figure 7. Plot of heat treatment temperature (°C) vs.

(time)? to fracture of cyclic anneals on thin films. The effect of substrate deposition

temperature, film thickness, and cut of the

silicon single crystal to the 111 planes on

the mechanical stability of the reacted film are major concerns in these studies.

* Lower substrate deposition temperature

49

Figure 8, Scanning electron micrograph of titanium thick film

surface (2.2 um) after cyclic anneal at 650 Cy total time of 2 hours. Magnification 100X; Tilt = 20°.

50

Figure 9. Scanning electron micrograph of titanium thick

film surface (2.2 wm) after cyclic anneal at 650 C, total time of 5 hours. The entire film flaked off at this stage of annealing. Magnification 100X; Tilt = 20.

51

Figure 10. Scanning electron micrograph of titanium thick film

surface (2.3 pm) after total annealing time of 5

1 hour at 625 C. Magnification 100X; Tilt = 20°.

52

Figure 11. Scanning electron micrograph of titanium thick film

surface (2.5 pm*) after cyclic anneal at 600 C, total time of 7% hours. Magnification 500X; Tilt = 20°.

*Lower substrate deposition temperature.

53

in the latter part of this chapter. A‘l1 other samples (described in

Section IV) had a spontaneous fracture point (see Figures 10 and 11).

The data collected on Figure 7 served in planning anneals for the

larger X-ray samples.

Optimum deposition temperature appears to be at 350°C since

greater interface instability exists in films deposited at 275°C. It

appears, as in mechanical fatigue, that an endurance limit may exist

allowing samples to be cycled indefinitely below this temperature.

Complete information on the effect of substrate cut, film thickness,

and surface roughness of the silicon substrate on the endurance limit

is not available. An attempt to retain the reacted structures after

one hour at temperature with a cooling rate of 3°C per minute resulted

in the same characteristic fracture at approximately 300°C. In every

case, fracture occurs on cooling after annealing within a well defined

temperature range. Most often the fracture correlates with measurable

Silicide formation.

Step and Isothermal Anneals

A total of eight two-hour diffusicn treatments at temperatures

from 350 to 650°C were carried out on a 2.2 micron titanium thick

film, cut to within one-half degree of the 111 planes. The first step

anneal was chosen at 350°C to facilitate comparison with the as-

received sample deposited under similar conditions. Subsequent

temperature increments were determined from cyclic arneals and general

observations of conditions allowing the metallic films to remain

adherent. Since the mechanical instability results from differences

in thermal expansions of the individual materials, the temperature

increment was systematically decreased as higher reaction temperatures

were approached. Systematic step anneal upwards from the deposition

| temperature indicated that X-ray line shift, line broadening and

elastic bending of substrate are influenced by silicide formation.

Tables IV through XII are a list of integrated intensities at

different two-theta positions of all diffracted intensity above

statistical background for each of the eight anneals. It should be

emphasized that very little high angle diffracted intensity is present

in these thick film samples. The computer simulations of these high

angle regions are only semi-quantitative and all foundations for a

diffuse model are based on the low angle regions. The half-widths

of lines lying at 26 positions greater than 50° are the only simulated

parameters in which confidence can be placed. Figures 12 through 33

are the corresponding computer simulations where the points represent

the experimental intensity. The individual simulated reflections

along with the summed intensity is displayed in each figure for

comparison of the fit. Table XVI lists the Pearson function parameters

for each step anneal. A modified Lorentzian (m=2) best approximated

the shape of the X-ray diffraction peaks throughout the anneals with

the one exception being the titanium (011) at reaction temperatures

of 600 through 650°C, where "m' equals five.

In order to measure the response of the elastically bent substrate

to silicide formation, optical interference measurements of the

deflection in the sample were made and the contours plotted on Figures

55

35a and b. The maximum deflection of the substrate decrease with

increasing diffusion temperature or time corresponding to increased

silicide formation. In contrast, Figure 36 displays the profile of

a 2.5 micron thick film cut to within three and a half degrees of the

111 planes. The convex profile suggests that orientation of the

silicon cut affects the amount of strain present in the film and thus

the mechanical stability.

An isothermal anneal for times of 15 and 30 minutes at 625°C

reflect the effect of substrate orientation on silicide formation.

Samples cut to within two and a half degrees of the 111 planes

exhibited a lack of appreciable strain in the plane of the metallic

film. Tables XIII through XV are lists of integrated intensities at

different two-theta positions for each anneal. The X-ray simulations

needed to determine the preferred orientation and resolution of the

silicides formed are presented in Figures 36 to 45. Once again, a

modified Lorentzian distribution sufficiently approximated all

diffraction peaks. Table XVII contains the parameters of the Pearson

distribution for each individual reflection observed as a contribution

to the total experimental intensity.

It is evident from each set of simulations for the step and

isothermal annealed samples that two distinct orientations of the

titanium are present although a strong basal plane orientation is

common to both. The isothermal annealed specimen contained a tensile

strain on the (010) prism planes and a compressive one along the basal

plane (002) which decreased with increasing diffusion time. Titanium

56

monosilicide (0.1 um) present at the interface was strongly preferred

in the as-received sample. The silicide thickness increased to half

a micron after treatment for 30 minutes and fractured on cooling from

a subsequent anneal for an additional 30 minutes (see Figure 9).

The fracture corresponded to the cyclic heat treatment analysis of

these specimens (see Figure /) and substantiated a previous conclusion

for the fracture mechanism.

The titanium film remained adherent throughout all eight stepped

anneals; however, cracks initiating at the perimeter of the sample

were present after the final treatment. The existence of titanium

monosilicide as a dispersed phase (see Figure 46) in the initial thin

film structure exemplified the dominance of grain boundary diffusion

and nucleation at 350°C. A step anneal at 350°C produced an

approximate doubling of the volume fraction of monosilicide contained

in the titanium, from two to five percent (see Figures 12-15). The

monosilicide was random in orientation during all anneals. and was a

constant volume fraction of the remaining titanium film. If the

monosilicide were a planar deposit at the interface, a 0.2 ym decrease

of the plating would be required. The simulation was forced to fit

at low angles, relaxing on the condition of "g" factors summing to

one and conservation of material, yet the nigher angle intensity

region failed to yield a reasonable solution (see Figure 56).

Annealing upwards from the deposition temperature resulted in the

formation of a planar titanium disilicide deposit (see Figures 47-49)

at the original titanium-silicon interface. A linear decrease of "g"

57

from the silicon substrate with increasing silicide formation was

observed (see Figure 54) in each subsequent anneal (see Figures 50-52).

The final treatment at 650°C resulted in a maximum thickness of the

disilicide (3.9 um) and the formation of a planar deposit of mono-

silicide at the titanium-disilicide interface (see Figure 53).

Uniform tensile strains in the plene of the titanium film varied

insignificantly for the crystallographic planes displayed in Figure

56 in this series of heat treatments. The prism planes (010), whose

(39) when compared to the (002) modulus of elasticity is ten smaller

and (011),.showed the largest Poisson's contraction in the planes

parallel to the surface. Correspondingly, the smallest non-uniform

strain (line broadening) was associated with the (010) planes which are

(40) the slip planes in titanium The X-ray strain data does concur with

the mechanical constants presented in tiat a low modulus of elasticity

for a given plane will display a large ’oisson contraction and less

non-uniform strain. Line brodening inc -eased with silicide formation

for all reflections of titanium.

The disilicide reflection remained sharp after all stepped anneals,

thus agreeing with the bulk sample whici found titanium and silicon

insoluble in TiSi,- In the completely diffused sample, the monosilicide

present as a film displayed additional line broadening, probably due

to the range of compositions found for chis silicide in the powder

study. A weak preferred orientation of the TiSi in contrast to the

9 layer, reflected the influence of orientation of the initial TiSi

distance from the single crystal silicon substate.

58

Table XVIII is a list of X-ray data obtained for a step annealed

sample, 2.5 microns thick and cut to within three and a half degrees

of the 111 planes. The absence of any appreciable silicide formation

indicated the lack of adhesion of the titanium film due to the lower

a O substrate deposition temperature of 275 C.

Conclusions:

ol. TiSi, was confirmed a C54 orthorhombic structure having correspond-

ing structure factor forms and lattice parameters determined by

this study. The compound is stoichiometric in composition exhibit-

ing no solubility of titanium or silicon in it.

TiSi is not stoichiometric at low temperatures; rather a range of

compositions and lattice parameters exist. Ti,Si, is a high

. te Oo temperature compound, absent in equilibrium below 1050 C.

The thick film reaction between titaiium and silicon differed from

that of bulk samples, forming a large planar film of disilicide

at the original interface. The disi:icide film decreased the

transport of silicon and a second re: ction product of monosilicide

formed at the titanium/disilicide inierface.

The dominance of grain boundary diffision and nucleation in a film

diffused at a temperature of 350°C was observed, forming a dis-

persion of the lower free energy moncsilicide. Temperatures of

(2) silicide formation were higher in previous studies because of

the presence of silicon oxide at the interface. The absence of

degassing in the thick films verified that the method of

preparation did eliminate the oxide layer on the substrate.

Mechanical instability of the film results from large thermal

expansion differences of the components and silicide formation.

The highly deformed nature, dependent on cut of the silicon crystal,

warrented the use of computer simulation analysis of the X-ray

diffraction patterns from the diffused structure.

Suggestions for Future Work

1. More detailed studies of the low temperature phase diagram for

the titanium-silicon system is essential in characterizing the

kinetics of silicide formation in thick film structures.

The effect of substrate orientations on silicide formation

temperatures and phases characteristic to each should be explored

holding the substrate deposition temperattre at 350°C.

X-ray data obtained at temperature should provide sharper

diffraction lines because of the absence of that mechanical

deformation which is prodtced about each interface on cooling to

room temperature. The intercomparison between at temperature data

and room temperature data should provide considerable information

on the deformation mechanisms which are active on cooling.

INTENSITY

10. OO

8. OO

6. OO

4.00

Z. OD

60

7 t i: + + —t {- t —— t — t -t- + — t +t t —+ t +

, &@

1 1 m u

+ } T

mn . A Ti (002)

| _ Ci a T

F}

| Ti (010) y / . 4

Sg 7 Gf o 2 coo . m

T ul 0 ~~

0 Nn 0,0 Q 7 m

QF ) 0

1 oo 0 +

: Q ¢—

0 0 | Q wh

W a

TiSi (210) TiSi (102) x . 4 \ Ti (011) +

| St 21) ;

<— : . > Sn — —

35 00 35 83 36. 67 37. 50 38. 33 39. 17 40. oO 40. 83 4\. G7 42. 50 43. 33 44.17 45. 00

TWO-THETA Figure 12. Experimental intensity simulation for as-received 2.2 um titanium-silicon thin film, 28 region from 35° to 45°.

INTENSITY

61

=—_

15 00 t—— tt ot tt Ht Ht tt tt} 1— t—— —

+ al

1200 7 4

+ {

9.00 7 1

| +

6.00 Ff a ° o Te 8

| 1

3.00 | Ti (112) ai

Ti (103)

| TiSsi (004) +

.0O a t = . _- .

70. OO 70. 83 7L. 67 72 5O 73. 33 74. L7 75 00 79 83 76. 67 77. 50 78. 33 79. L7 80. 00

TWO-THETA . . . . O oO

Figure 13. Experimental intensity simulation for as-received 2.2 micron titanium thin film, 26 region from 70° to 80°.

INTENSITY

10. GO

8. OD

6. 00

4. 00

2. OO

62

Figure 14.

TWO-THETA

Experimental intensity simulation for step anneal for 2 hours at 350°C, 280 region from 35° to 45°

{——++ +——+ {+ t +- ae + + +——++

4 fu) +

o, f

vy

4 ih iP r

f \ 1 F |

i, iT}

T + rf iF) rr

1 oy 4 .

y ]

C ‘ w

1 wd AO 4

er O . @ 7 m 4 a QP UO iu _

(¢]

0 ba) t Ti (010) Soa © 6

Ti (011) - —_J

a TiSi (210)

oo fist (211) L

_ | \ a "|

35 00 34 83 36. 67 37. 50 38. 33 39. L7 40. GO 40, 83 41. 67 42 50 43.33 44.17 45 00

INTENSITY

1& 60

12 00

3. 06

6, 06

3. 06

63

{ +- t t t t t t t —t t t t— t— t i —t —t t t

I _

Ti (020)

: Ti (103) "|

. oo ao (112)

| \ a __--TiSi (004)

7Z GO 72 SO 73 00 73. 50 74. GO 74 50 75 0O 7& 50 78. GO 76. SO 77. CO 77. 50

Figure 15.

TWO-THETA Experimental intensity simulation for step anneal for 2 hours at 350°C, 28 region from 72° to 78°.

78 00

INTENSITY

145 00

12 00

3. OO

6. 00

3. OO

64

+ ~~

~~

—_

=e

a

-~

—

45 00

Are

Ti (002) ae y of

fy) :

- -

} i m

= Pf eo

C)

(yp i m

ae Ms o 4 LS —

a 0 a iT} ad

. ha]

f oF ) u slog y A o 8 ao e

4 ul Dnm8 ul a < \ fi Z ) oO u

> 2 ex é, Oo a

1 _ OF 2 +

i TiSi (102) . Tos ta Ti (010) Ti (O11) Wl TT

we On

+ , —— TiSi (211 ie TiSi (210) a )

\ fo TiSi, (004)

1 . a Tisi, (022) 4 . 7 2

35 00 35 83 36. 67 37. 50 38. 33 39. 17 40. OO 40. 83 41. 67 42. 50 43. 33 44.17

Figure 16. Experimental intensity simulation for step anneal for 2 hours at 450°C, 280 region from 35° to 45°,

INTENSITY

1§ DO

iz 00

3. OO

6. 00

3. OO

65

t —t t t t t t t t —t t t t t t t —t t 7

a ai

| - Ti (200) | Tisi (412) — TiSi (004) _

TiSi (501) - a ~ . TiSi, (333)

A _N y Lo “TiSi, (026)

72 OO 7Z 58 73.17 73.79 74. 33 74. 92 74 50 76. 08 76. 67 77. 295 77. 83 78. 42 72.

Figure l/.

TWO-THETA Experimental intensity simulation for step anneal for 2 hours at 450°C, 26 region from 72° to 79°,

INTENSITY

15 00

12 00

9. OO

6,00

3. OO

66

+ t t t t t t t t f —t t t t t t f f { t t

; Ti (022) Ha + oN .

\ a a

4 \. oy m 4.

\ 2 \ 0

n A “

- Tisi, (311)

Ti (016) —~_ TiSi (102). J oN -—T

‘\ .

oR Ti (011)

f v | 7

| | 7 fr} \

Q 2 RD na —~L

TiSi (210) 5 ) Ca ae “8p } am, nh a 2 TiSi (211)

otf us ' 7 ne

7 ye Le ~ Oe = p- Q) m

{ Cj CF wt u eS

\ fo oN TiSi, (004) \ a OOO aa |

a 0a rn" a © )

SE (022)

_ —_ ™ eee EE |

35. 00 35 83 36. &7 37. 50 38. 33 39. 17 40. 00 40. 83 41. 67 42. SO 43 43 44.17 45 00

TWO-THETA Figure 18. Experimental intensity simulation for step anneal for 2 hours at 500°C, 28 region from 35° to 45°.

INTENSITY

67

“ +

| ao

4 4

LS 00 t t t t — +— {———_t t t -t t t— t

4 +

1200 7 T

| al

goo - |

500 92 age ;

[ Tisi (412) —_ Ti (200) T

TiSi, (333) --~_ 7 3. 00 1 2 ” / os r ~~ ZL “nisi (004) TiSi (026)

Tisi (501) aa

| ao ~ | . a“

. oO { t T t ——f t t + t tT T { t —t T ——— t —t t— / —t t

72 CO 72 58 7317 73.75 74 33 74. 92 7a 50 76. 08 76. 67 77. 25 77. 83 78. 42 79. GO

TWO-THETA Oo . Oo O

Figure 19. Experimental intensity simulation for step anneal for 2 hours at 500 C, 26 region from 72° to 79 .

INTENSITY

14 OO

12 00

3. OD

6. OO

3. OD

68

- t r—t —t +——t t t + — t t — t t + —t t

+

frye

i)

4 a

\

| be ch

C" J

ui

+4 cy

rr ie

r

4 r , ‘Ti (002) Tisi, (311) —_ f v a

7m

5 Q

S oO "

| q L fr ©

an ty OTIQ Com Ti (O11) ate! © a T4 (010) A A CT of J om

- yo o Ne at a en aS (301)

t 2 AAC hh, ROS /. ; Qn

eal Ml tas Al San _———TiSi, (004) . Pr (yu / oO SAMEN. 2

TiSi > a ae a | TiSi (210 St , iSi (210) (102) :

36 00 38 92 36. 83 37. 75 38. 67 39. 58 40 50 41. 42 42 33 43 25 44. 17

Figure 20. Experimental intensity simulation for step anneal for 2 hours at 550°C, 26 region from 35° to 46°.

INTENSITY

69

— A + 7

1S oO t t t t t t i t t t —

12 00

3. OO

‘Ti (200)

6. 09 | oo T ?

TiSi (501) ~_

TiSi., (333)

| \ 4 3. OO TiSi (412) ‘. iSi , Tisi,

(026)

Wen t t t t t — ' —— ! i ———t —

72 GO 72 58 73 17 73 79 74. 43 74. 92 72 50 76. 08 78. 67 77.25 77,83 78 42 79. OO

TWO-THETA Figure 21. Experimental intensity simulation for step anneal for 2 hours at 550°C, 28 region from 72° to 79°

INTENSITY

14, 00

12 00

3. 0G

6. OG

3. OD

70

t { t t — —+ + + t t— { t t t t t -t t t t t t t

wae

: bi T

m7

A 7 me

Tisi, (311) 9 | ae . rua) |

NS

a u 0

| 0 | m pH

4102) ___-- Ti (002) 1 TiSi (102 | a al

ee a

™

1 Ti (010) TH (011) a

\ Lo ‘

J Tisi (210) NN , C TAS (211) +

me cry fy UN Gi OO .

(ane “ \ is 08> DO me Kone Md a

Re it Y u

4 oe x DOM m OQ” Lo Qo eo TiSi, (004) at

J / yD a

tpAnTbaae” | a ee / / “ Ou C iy TTR

TAT d 4 ’ uy () A (" A

<a. = pw TEST) (022)

354. G0 35. 83 38. 67 37. 50 38. 33 39. L7 40. 00 40. 83 41. 67 42. 50 43. 33 4417 45 00

TWO-THETA


INTENSITY

1& 00

12 00

9. 05

6, OO

3. OD

71

t t t t t t t t t — t t t + t t t t t t t

©

art +

ys m

fo a

Oo D 7 c us a a aus >

* w

| a a oer SS a mang2e om :

4 cy rm WN

a “2. 0 m

a "oO ao oO oD woo

+

[i (200)

+ —

| TiSt (412)\ Tisi (501) | \

Ti (103) TSI, (333) -

oo _-— Ti (112) — f |

\ 7 TiSi (026)

\ aw —_

— t -—— t + -— i = t t t t t —<——} —— { >=

72 OO 72 8 7317 7375 74. 33 74. 92 75 50 76. 08 76. &7 7%. 25 77. 83 78 42 72. GO


INTENSITY

19. 00

15,20

ll. 40

7.60

3. 8B

72

t + { t t t t t —t — t f t t t t t t t

si _ C 4

" a

") + ui a

m C]

~oTiSi, (311)

4 Ti (002) 4

A _Ti (011) 4

ee TiSi (211)

4 Lf oy _

t TiSi, (004) “2 2

fhe / BEM OMB—p—m |

ST @—_H <M TASi, (022)

35 00 35 92 36. 83 37.75 38. 67 32. $8 40. 50 41. 42 42 33 43.25 44. 17 45 06 46. G0


INTENSITY

16. 8D

12 60

8. 40

4. 2B

73

/ ~TiSi (312) |

4 +

TiSi, (131). TiSi (410) - TiSi’ (511) 4

4 -4

—— t i + t t t i t t t —

68. 00 58. 98 So. 17 So. 7S 60. 33 60. 92 6L. SO 62 08 62 67 63 25 63 83 64. 42 6S OO


INTENSITY

21. OO

15. 80

12 50

8. 40

4.20

74

t —+ t t + t — t t t — — t { t +- I t t t

a

oye fs

“i A

OE] 1 ° o SOL

ASO BOON A a OTT " Ne 2 Ove a

a BItt nm 2 , ND ligigugugamunu eee TL (200): SOR COT

TASd (412) — 7

TiSi (501) \ TiSi, (333) T 103

TiSi, (602) #03) :

. Ti (112)

7 TiSi, (026) T

71. OO 71. 67 72. 33 73 00 73. 67 74. 33 75 00 79 67 76. 33 77. 00 77.67 78 33 79. BO

TWO-THETA


INTENSITY

19 00

14 20

Ll. 40

7,66

3. BD

75

46. 00

Tisi, (311) we

N ey

u

‘ CS

TiSi (102) fs oN

QO aa (002)

Ti (010) o

Tist _ Ti (011)

+ (210) ~~~ 4

TiSi (211) 4 an ~

eT

aes \ ‘SS

mene \ NSO, ———TiSiy (004) PRAgsTre \ BB aa | |

a SOON ae a a Q TiSi, (022)

35 00 35 92 36. 83 37.79 36. 67 39. 98 40. 50 41. 42 47. 33 43.25 44.17 45 08

Figure 27.

TWO-THETA

Experimental intensity simulation for step anneal for 2 hours at 625°C, 28 region from 35° to 46°.

INTENSITY

Zl. OO

16, 60

12 50

8. 40

4. 20

76

T

|

4 TiSi (312) +

| TiSi (410) |

59. 00 59. 33 59 67 6&0. OO 60. 33 60. 67 61. 00 61. 33 61.67 G2. 0O 62. 33 G62 67 63. 00

TWO-THE TA

O Figure 28. Experimental intensity simulation for step anneal for 2 hours at 625°C, 20 region from 59° to 63°.

INTENSITY

ZL. OO

16. 80

12 60

8. 40

4. 20

77

a

4 UI _|

A)

CN

a "

Ao UB OO O iF, 7 T

Oh On if . te m7 (4

LF | v Sop goo ln , v. Roy |

nooo Oo no She

oO Shy ty Gag “ag pooo® -—Tisi, (333) erm = “Qoaanammmd 7 TiSi, (602) +

Ti (112)

t So TiSi, (040) -TaSi (223) 4 TiSi (501) ____ a nS (421)

TiSi (412) Y .

Ti (103)___ /

TiSi (230)

\

= ' +

«KN

= SON,

70. GO 71.50 73. 00 74, 50 76. GO 77. 50 793. GO 80. 50 82. 00 83. 50 85 G0 86. 50 88. 00

TWO-THETA Oo . oO oO

Figure 29. Experimental intensity simulation for step anneal for 2 hours at 625°C, 26 region from 70 to 88.

INTENSITY

13. OO

1520

il. 40

7,60

3. 8D

78

t

1 2 . Ma

—_

TiSi, ere a

\ 7)

. +

—-—Ti (002)

| TiS (102) o 7

Ti (011)

T Tisi, (113)—_ J

‘TiSi (211) - Ti (010) a Lo 4

os = iSi 004 TiSi (210) N fre, aa iy (004)

- )

5 Vigan as 4 1) +

tae ry ph, ug ph

TiSi (111. TiSt (002) a +t Mean / Rm, OU TiSi, (022) we — fs \

Qa 7

A ptm 4 (rh ua Poor OOOO eg ‘On "|

oO \ \ ! i? (RSs eee

| ——~ Ss SES |

32 00 33. 17 34. 33 35 50 36. 67 37. 83 39. 00 40. 17 41. 33 42. 50 43 67 44. 83 46. GO


INTENSITY

79

T

16.80 7 T

12 60

B40 7 +

TiSi (312) TiSi (410) 60. 00 60. 60 6L. 20 61. 80 62 40 63 60

TWO-THETA

Figure 31. Experimental intensity simulation for step anneal for 2 hours at 650°C, 28 region from 60° to 63.

80

TWO-THETA


21. oO t t t t t t t t t + t t t t t t t + + t t t

+ -

AS a 16,80 —

u ub

" \ | T . 7

° © > 0 q [- + m © m u u > 4

4 1? 60 7 oD Th Uren nanmoe® a

YY) os ° ~ thee Lon v op |

= , ee SOUT rr tresadt

Lu boaae

- — < 68.40 4 a Tisi, (333)

: TiSi (412) .

TiSi (501) oa‘

4.20 | AN TiSi (004) Ti (103)

oo .Ti (112) |

<> Se _ oN. . co “ Tt t t i t u T t a tr —— — =_— T t + t r t t t t

72, OO 72. 56 73.17 73.75 74 33 74 92 79 50 76. 08 76. 67 77.25 77. 83 78 42 793. GO

INTENSITY

16. 80

12 60

8. 40

4. 20

81

t t t t 4 + + t + t — + t——_ + —t—— t t t t——t t-

| T

+ +

+ 4

TiSi (223)

| Ti (202) aS (230) |

82 00 82 42 82? 83 G3.25 83, 67 8+. 08 8&4. 50 84. 92 85 33 85 75 86. 17 86. 58 87. 00

TWO-THETA


82

*poqtsodop

SCM WIT}

WNTURITI

94. YOEYM

UO sOeFJANS

VY} SBEOTPUT

MOITIe TBOTISA

*SaTsue VYSsTA

Je usyZeJ

azeAASQGNS UODTTTS

ay

FO

SUTpuseqd

IIASeTe

9Yy} paansesauw

sanbruyoeq

souaTaTAaqUT

Teotadg

‘yrE

ain8tTy

(°WO)

9F0ueIsSTG

T°t c°

7° €°

co" T*

0 Te

mn, v

4 4

T T

a -

T

°

9,059

L. z°

9,068 ——\-—-

L qe"

- |

3,00 —

i"

L _

(°TFW) OT X Your

83

*poejqtsodep

SCM WTF

WNTUeAT}

ey

YOTYM

UO BdeJANS

9Yy Sa2ReOTPUT

MOIIe

Te°TIPA

«“*SaTBue WUSTA

Je Useye

|}eAISGNS

UODTTIS

3syW jo

BUTpueg

DTISeTS

sy} peanseow

saenbruyds}

souaTazZAaquT

Teotjdg

(°WO) soueIqSsSTd

‘qve einsTy

TT see

(THM) OT * your

84

as received

as

received

Po,

Figure 35. Optical interference technigues measured the

elastic bending of a silicon substrate cut to

within 3.5° of the lil planes. This graph contains measurement: taken at right angles

to one another for tro step anneals. Vertical

arrow indicates the surface on which the

titanium film was deposited.

INTENSITY

85

15 oo t t t t t t +t t +t +— t t t t t +- t t t +

Ti (O11

12 00 | TE (002) ae - ° \ A T “ ,

oo \ my

m7 a

FI

9. OO T 7

Qo

}

Ti (010) 1

6. OO T 7

rj

ma

4 - —

th 7

3. OO T 7 ©

a Q © ~~

a Q +

re Oe ee eer erertr ty 6 Hm 2 OO O»yrrrerrenernta

. OO t t t { + t f t —t- t | t { t f —r —t

34. 00 34. 57 35 33 36. 00 36. 67 37. 33 38. 0O 38 67 33. 33 40. 00 40. 67 41.33 42. 00

TWO-THETA

Figure 36. Experimental intensity simulation for as-received, 2.3 um titanium thin film, 26 region from 34° to 42°,

INTENSITY

86

soo 7 — { t t t t

/ +

12 ao 7 T

9. OO T L

6. OO T 7

q

ao o )

3. OO T a Ti (012) +

| |

. OO t “+ ' T t t ' t q

52 00 52. 40 52. 80 53. 20 53. 60 54 00

TWO-THETA

Figure 37. Experimental intensity simulation for as-received, 2.3 um titanium thin filn,

28 region from 52° to 54.

INTENSITY

87

15 oo t t t t t t t t t

iz00 7 T

3. OO | T

6. OO

(110)

3. OO 7 oo a

. OU T t t t t t t t a

62. 0O 62 40 62. 80 63. 20 63. 60 64. OO

TWO-THETA

Figure 38. Experimental intensity simulation for as-received, 2.3 um titanium thin film, 28 region from 62 to 64.

INTENSITY

88

15 00 -——- t t t { t + t t + f — t t t t + t ——

4 4

1200 T +

|

4 ASR _ + 9. OG af Un

TARR ) i) A

m A FF ny 7 c ty 7 m P pF} 7 N -

: oF eg rc a po) CI HoOMoMAwp- Mi Kon yy

0 OOCARSASSSSGR Sea DamoAa aaa ome ~ TABOO ORAMAAmAMAMewBer ©

DOVAAMM

6. OO ; T

| Ci (201) |

: Ti (004) L

. Ti (112)

3. 00 r |

| Ti (103) :

_ en 4 3 2 i 1 1 , 1 4 4 1 4 4 1. 1

. oO q qT 1 v 1 i t t | ' T 4 qt ' Oo t { of 1 T t

70. 00 71.17 72 33 73.50 74. 67 74 83 77.00 7817 79. 33 80. SO 81. 67 82. 83 84, 00

TWO-THETA . . . O O

Figure 39. Experimental intensity simulation for as-received, 2.3 wm titanium thin filn, 28 region from 70° to 84.

INTENSITY

30. 00

24. OD

18. 00

1z 00

6. OO

89

4 t t t t + t —t t t t t ——- t t t +t t t —t

u

Ti (002) —- ae ;

m

Ti (011) -

| 4 oo

ff

n 4 ; _

1 t - Ti (010)

Oo W a u am

Ua ua

T ua + DR .

/ 0 Fr . ra Q Q m

6-B--2r-F- [ OUTST Fe he hee)]nod © 8 8a pou U 8 Q Q OVW rae Re +

34. 34. 67 35. 33 36. 00 36. &7 37. 33 38. 0D 38. 67 33. 33 40. OO 40. 67 41. 33 42. 00

Figure 40. Experimental intensity simulation for 15 minute anneal at 625°C, 26 region 34° to 42°,

TWO-THETA

INTENSITY

15 00

12 0

a. OB

6. OO

3. 0D

90

ao (201) a

i. 1 4 4. 4 4.

v 4 q { t t '

75 00 75 GO 76. 60 77. 40

Figure 41.

TWO-THETA Experimental intensity simulation for 15 minute anneal at 625°C 26 region 75° to 79°,

78. 20 79. 06

INTENSITY

145, 00

1Z BO

9. OD

6, 06 Ty

3. OD

91

TiSi (421) ee eel (004)

80. 00 80. 80 81. 60 82. 40 83. 20 84. 60

Figure 42.

TWO-THETA

Experimental intensity simulation for 15 minute anneal at 625°C, 28 region

from 80° to 84°.

INTENSITY

25, 0D

20. OD

1& 0D

10, OO

3, OO

92

+

_~-

+— + t f t —+- +—- t t — t t +- t f t t am i t—

by)

4 2

Ti (002) ———__ 7

m

r Ti (011)

+

—

iy

{ : +

uw

4

| | af

" u

4 J

. Ti (010)

5 a ° J r a . TiSi (002) eH p O .

a 7 0 f

{ a owes & 82 Owe sess

34. CO 34. 67 35 33 36. OD 3b. &7 37. 33 38. 0D 38. 67 39. 33 40. 00 40, 67 41. 33 42. 00

Figure 43.

TWO-THETA

Experimental intensity simulation for 30 minute anneal at 625°C, 28 region from 34° to 42°,

93

: | : 7 20. GO

16. 00

12 00

6. OO

INTENSITY

4. 00 59. 60 59. 60 60. 20 60. 80 BL. 40 62 00

TWO-THETA

Figure 44, Experimental intensity simulation for 30 minute anneal at 625°C, 26 region from 59° to 62°,

INTENSITY

10. OO

8. OD

6, OO

4, OO

2. OO

94

f t— +— f t t— t —t+ —+- + t +— t —+- t — —+ t ti———_r AO

4 m |

u

yp ©

m Nc)

5 AC rw 3 T

MW HS ry n 7 ai ©

fe @ Gh mat f - DQ OD OCP Se ee eee MMR MnMAMOMOMMOMNMMD?In Q

NO OOM PPSEseBoeonMAADonoOaeBan

Q t oT

+4 -

+ 4

TE (201) Ti (004) ~

TiSi (421) ~.

i a Ti (103) Ti (112) mo, al

4 4+

70. OO 7L. 08 7Z L7 73.25 74 33 74 42 76. 50 77. 58 78. 67 79. 74 80. 83 Bl. 92 83. 00

TWO-THETA

Figure 45. Experimental intensity simulation for 30 minute anneal at 625°C, 26 region from 70° to 83°.

95

——=~Monosilicide

Titanium

! \ — - Ay i poccd) = 2.2—uM

| '

Silicon

bo

Figure 46. Illustration of cross-section of thin

film structure for as-received and 350°C

step anneals for 2 hours.

Figure 47,

96

a Titanium

Monosilicide

Silicon

oC

2.1uM

Tilustration of cross-section cf thin

film structure for 450°C step anneal for 2 hours.

-5uUM |

97

Titanium

Monosilicide

|

NN

4 ' ' | ' ' 1 if U '

Lut LL pet pa Reel = - 1 ' \ { ' \ \ aie ioc roo4 --- <1 2.0uM

i i —. ! ‘ | | r /| i

' | | | | L | 1 i

Disilicide op

\

Silicon

Figure 48.

Mo

Tllustration of cross-section of thin

film structure for 500°C anneal for

2 hours.

1.0uM

98

Titanium

fo a Momost Hicide

\ fi! i ; d 1 Le ee ---- ee r--

; J ‘ i 1.8uM

| poste te Hep Le i ) | | \ LJ

Disilicide nN

)

|

j = Silicon G=4.5

i

Figure 49. Tllustration of cross- section of thin

film structure for 550°C step anneal

for 2 hours.

99

Titanium

Monosilicide

i j j i Ha-—) ff L--- i- -¥ - 4 oped

| rool I~ 4 oT} ro 1.6uM

a: L a re Pr |

1. 5uM Disilicide ce 3.6 tH ~

geass

Silicon

Figure 50.

——__

Tllustration of cross-section of thin

film structure for 5750C step anneal for 2 hours.

100

Titanium

Monosilicide

=|

dim be — —— — SO «a Disilicide

Silicon

es Figure 51. Illustration of cross-section of thin


for 2 hours.

101

Titanium

an

Monosilicide

1.0 iM

T 1 j i i t { ' Lm my —~--4 i- 4 ---1 rnd

’ ‘ \ ' ' \ t a . ‘ . a

| <— —|—ce2.5

G=3.2 Bebe Fp

| Disilicide « |———G=4.5

Silicon

ae _—

Figure 52. Illustration of cross-section of thin film structure for 625°C step anneal

for 2 hours.

102

Titanium

Monosilicide

-4M so r ] és FF Gf fot

é H

; G=1.2 |

G=2.5

G=3.2 _ ee — —} 3.9uM

G=3.6.— —_ — —. _—— — —e — awed

Disilicide G=4.5

Silicon

Figure 53. Tllustration of cross-section of thin


for 2 hours.

G FACTOR

3, 00

4, 00

3. OO

2. 00

1.00

103

CO 8 1.60 Z2. 43 3. 20 4.00

MIIRONS

Figure 54. Plot of "G" factor vs. disilicide thickness in

final step anneal treatment at 650°C for 2

hours. These points represent an average "G" factor for each thickness.

OTRAIN

104

CO 6000 120.00 180.00

_070 { { i t f t t t =f

Ti (O10) fo tL (

: 8 o o . O58 m Go 8

. 045 : T

a Ti (011) +

aoe Ok Ti (002) x t

fs A T rm KO

A A “A 4 x

. 022 7 T

-olo + —t i—— i !

240.00 300.

TEMPEF ATURE

Figure 55. Plct of strain vs. tc aperature increment abc re deposition temp :rature perpendicular

to the crystallographic planes in step

ann2aled thin films.

O06

INTENSITY

10. 08

8. OO

6. OO

4. 00

2. OO

105

TiSi (004) g = ae

Ti (200) g=1.1 .

\

\

1 \ T \

TiSi (501) g = 2.0 \

| visi (412) g = 1.4 |

| \

Se v f f f t —t f == t t i t t > —t + t T —— t t

72 OO 72 50 73. 00 73. 50 74 OO 74 50 74 00 7% 50 76. CO 76. SO 77. 00 77. 50

TWO-THETA O, . . arr .

Figure 56. Experimental intensity simulation for step anneal at 350 C for 2 hours, to illustrate the location of monosilicide in

this film. Titanium thickness = 1.9 um.

7& GO

106

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III

(Continued)

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26

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9,

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166

TABLE XVIII. Thin Film Specimen 2.5 Micron of Titanium Cut Within 3.5° of the 111 Planes Annealed at Various Temperatures for 2

Hours, Measured at Room Temperature

28 26 26 26 20 28

Identification Cards As Rec. 350 450 500 550

a Ti (300 129.80 - - 129.7% 129.7% 129.6%

TiSi (610) 94.97 - - - 94.94 94.97

a Ti (202) 86.71 86.5* . 86.5% 86.6% 86.6% -

a Ti (004) 82.28 - - - 82.2% 81.9%

a Ti (201) 77.32 77.24 77.25 77.29 77.25 77.30

a Ti (112) 76.29 76.16 76.05 76.16 76.11 76.12

a Ti (200) 74.26 74.11 74,01 74.04 74.05 74.10

a Ti (110) 62.96 - - 62.88 - 62.78

oa Ti (011) 40.15 39.99 40.01 40.01 40.01 40.03

a Ti (002) 38.40 38.23 38.17 38.16 38.16 38.11

TiSi (210) 36.88 - - - - 36.87

ao Ti (010) — 35.06 34.92 34.97 34.97 34.97 35.00

Rel. Rel. Rel. Rel. - Rel. Rel.

Inten. Inten. Inten. Inten. Inten. Inten.

Identification Cards As Rec. 350 450 500 550

a Ti (300) 4 - - 16 16 11

TiSi (610) 10 ~ - - 10 15

a Ti (202) 2 1 1 4 1 1

a Ti (004) 2 ~ - - 4 5 a Ti (201) 14 8 16 19 18 16

o Ti (112) 17 2 7 10 8 8

a Ti €200) 2 1 7 9 8 9

a Ti (110) 18 - - 2 1 1

a Ti (011) 100 88 2/ 30 32 29

a Ti (002) 26 100 100 100 92 93

TiSi (201) 20 - - - - 20

a Ti (010) 30 21 91 92 100 100

*Determination of peak position better than one decimal place was not

possible.

Identification

Ti R

TiSi (610) Ti

Ti

Ti

Ti

Ti

Ti

Ti

Ti eerkreekk eee

TiSi (210) Ti 2

*Determination of peak position better than one decimal

(300)

(202) (004) (201) (112) (200) (110) (011) (002)

(010)

possible.

As

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Rec.

167

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REFERENCES

1. Balluffi, R. W. and Blakely, J. M., "Special Aspects of Diffusion in Thin Films", Thin Solid Films, 25, (1975), pp. 363-392.

2. Bower, R. W. and Mayer, J. W., Appl. Phys. Lett., 20, (1972) p. 359.

3. Mayer, J. W. and Tu, K. N., J. Vac. Sci. Technol., 11, (1974), p. 86.

4. Picraux, S. T., 'Mass Transport Between Two Metal Layers as

Studied by Ion Scattering", 6th International Vacuum Congress, Kyoto, Japan (1974).

5. Tu, K. N., Electrochemical Society, Extended Abstracts, 1, Vol.

116, (1975), p. 267.

6. Chu, W. K., Krautle, H., Mayer, J. W., Muller, H., and Nicolet,

M. A., Appl. Phys. Lett., 25, Vol. 8 (1974), p. 454.

7. Chopra, K. L., Thin Film Phenomenon, McGraw-Hill, New York,

(1969), p. 266.

8. Campbell, D. S., in L. I. Maissel and R. Glang (eds.), Handbook

of Thin Film Technology, McGraw-Hill, New York, (1970), p. 12-13.

9. Gangulee, A., Acta. Met., 22, (1974), p. 177.

10. Dearnaley, G. and Hartley, N. E. W., Phys. Lett., 46a, (1974) p- 345.

ll. Cotter, P. G., Kohn, J. A., and Potter, R. A., J. Amer. Ceram.

Soc., 39, (1959), p. 11-12.

12. Laves, V. F. and Wallbaum, H. J., Z. Krist., 101 (1939), p. 78-92.

13. Kato, H. and Nakamura, Y., Thin Solid Films, 34, (1976), p. 135- 138.

14. Schob, 0., Nowotny, H., and Benesovsky, F., Planseeber. Pulvermet.,

10, (1962), p. 65-71.

15. Svechnikov, V. N., A. Kad. Nauk, SSSR, 193, No. 2, (1970) p. 393.

16. Burkl et al. Monatsh. Chem., 92, (1961), pp. 781-88.

17. Nat. Bureau of Std. Circular, 539, 8, 64, (1958).

168

18.

19.

20.

21.

22.

23.

24.

25.

26.

27.

28.

29.

30.

31.

32.

33.

34.

169

S. S. Lau, W. K. Chu and J. W. Mayer, "Evaluation of Glancing Angle X-Ray Diffraction and MeV,He Backscattering Analyses of Silicide Formation", (submitted to Thin Solid Films, March, 1974).

Hutchins, G. A., Shepala, A., Thin Solid Films (to be published).

C. R. Houska, J. Appl. Phys. 41, 69 (1970).

C. R. Houska, High Temperature - High Press, 4, 417 (1972).

Houska, C. R., Thin Solid Films, 25 (1975) pp. 451-464.

James, R. W., The Optical Principles of the Diffraction of X-Rays,

Vol. II, The Crystalline State, Cornell University Press, Ithaca,

New York (1965).

Guinier, A., X-Ray Diffraction in Crystals, Imperfect Crystals

and Amorphous Bodies, W. H. Freeman and Company, San Francisco

(1963).

Harris, G. B., Phil. Mag., Ser 7, Vol. 43, No. 336, Jan. 1952,

pp. 113-123.

Elderton, W. D., and Johnson, N. L., "Systems of Frequency Curves",

Cambridge Press, New York (1969) pp. 77-78.

Hall, M. M., Veeraraghavan, V. G., Herman, Rubin, and Winchell,

P. G., J. Appl. Cryst., 10, (1977) pp. 66-68.

"Thermophysical Properties of Matter", IFI/Plenum Data Company, Division of Plenum Publishing Gorporation, New York, New York

(1975).

Schultz, L. G., J. Appl. Phys., 20, 1030 (1949).

Ventron Corporation, Alfa Products, Danvers, MA.

Dietrich, F., Smith, T., and Houska, C. R., J. Appl. Crystallo-

graphy, to be published.

Siemens America, Incorporated, New York, New York.

Diffin, W. J., Parthe, E. and Norton, J. T., Acta. Cryst. 17 (1964) p. 450-451.

"International Tables for X-Ray Crystallography", Kynoch Press, Birmingham, England, Vol. IV (1959) p. 74,76.

35.

36.

37.

38.

39.

40.

170

"0S/8 Handbook", Digital Equipment Corporation, (1974) Section 1, p. 93-97.

Ageev, N. and Samsonov, V., J. Neorg. Chim. 4, (1950) p. 950.

Hans-Ulrich Pheifer, Schubert, K., Zs. Metallkunde, 57 (1966) p. 884.

"Tnternational Tables for X-Ray Crystallography", Kynoch Press, Birmingham, England, Vol. III (1959).

"Handbook of the Phyicochemical Properties of the Elements", edited by Samsonon, G. V., IFI/Plenum, New York, New York (1968) p. 388.

Anderson, E. A., Jillson, D. C., and Dunbar, S. R., Trans. AIME,

197 (1953) p. 191.

APPENDIX I

Automated Texture Diffractometer

(29) Computer controls allow the automated texture diffractometer

to operate continuously without the presence of an operator. The data

collection technique is continuous, measuring diffracted intensity over

an increment of angular region rather than conventional step scanning.

The computer incorporates relative angular positions rather than abso-

lute values in execution of any movement. The purpose of this appendix

is to describe the operation of the following data collection programs:

1. CH.RL — operated with a chart recorder in the usual collection

of x-ray data.

2. "Search" - quickly collects data to identify angular regions

of interest.

3. RSCAN.RL ~— will provide integrated intensity, mean and

variance with scanning speed from 1° to 1/100° per minute.

Bringing the System UPY

The data collection system consists of two Sykes 7100 disks and

a PDP 8/e minicomputer which are interfaced into a timer-scalar and

stepping motors on the Siemens diffractometer. The following prepares

the system for operation:

"Refer to PDP 8/e small computer handbook pg. 3-1 to 3-5.

171

172

1. Insert the system programs disk which is placed with slot to

the back in the upper Sykes unit, push in, and lower cover

to the vertical position.

2. Insert the data disk which is placed in the lower Sykes unit

as above.

3. Turn the key switch on: the PDP 8/e (left side) to the power

position (center) (see Figure 58).

4. Select the appropriate terminai, either teletype or teleray

by switches directly above the PDP unit (see Figure 57).

5. Activate terminal

a. Teleray - turn switch on left to desired brightness,

position middle two switches down and all others to the

middle on box above terminal.

b. Teletype - turn switch on right to "Line".

In the event of a line power interupt to the computer, a boot strap

load (see next section) will be necessary if the following results in

no response from the computer. Initiating the system (first five keys

up, O through 4, refer Figure 58) is accomplished by:

1. Place HALT button in "UP" position.

2. Pressing ADDRESS LOAD, CLEAR, CONTINUE, on the right of PDP 3/e.

which results in a dot display on the active terminal.

Boot Strap Load

If a 7600 start has failed, the following load will bring the

system up without damaging any system programs. This must be loaded

on the switch register of the PDP 8/e in the following order:

"yoezr 9/8

ddd 9y}

uo Toued

uoTIoOeTes TeuTwAze,

‘fg eAinsTy

173

NAY

;LYOs7; NO

|SLIOA|SLIOA|SLION

TIVANVAAYANVAIYOLOW)

SI+ G+

E+

1H O71

qgAaw

ONINGNSE

3dVv SLHOIT LYOddNs

YAMOd

SSA INN

3SN

LON

OG Q33dS YOLOW

AAO 440

UOT IIeTAS

QO Teuluarsy]

AesoyaL ALL

174

GON _|

193738

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3/8 ddd

* gg oan8Ty

| |

d31S

A300

SKIS omens

4NO0D Vyeana

tj

Luvs

|

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ayvay

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fotsfelz[s]}s[ele HTS

YSLSIOSY

HOLIAS

fe aul

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aw

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SLVisS

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000

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000

000

000

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| |

| L[/

ww |

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1)}p

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WVYdH9Odd

ONILNDSAXA

S! YSLNdWOD

LZ

LHOIT AYOWSAW

QSQN35LX4

//

175

1. Pull switch "4" up, press "ADDR LOAD", key down (all others

are down).

2. Enter the following numbers by pulling up the appropriate

keys and pulling up the "DEP" key after every set is

entered:

1127 6731 6731 7600 6732 5204 6734 7106 7006 3232 6734 7012 7012 0226 1232 3631 2231 2230 5204 1203 6731 5014 0017 0401 7400 0000

So

NR

NM

NN

we

©}!

Oo he

|

BW

h

wo CS

we w

“

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OU

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v wow

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iv)

w w

w w

1 ,5,7,8,11

oO Pe

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AMOR EPLERRE

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wow

a

HH

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FOC

OCrFOOCOCOCOCOCO CO

bh vue

ee

ee

lll

lhl lll

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HN PNP

RP RP

NMRFPRP ENP PRE >

fea

v w

w we

« w

vt

we

\ iv

vy

w vw

\ wT

wy

At this point, go back and check the locations and corresponding

entries. This procedure is listed below:

1. Pull switch "4" up (all others down). Press "ADDR LOAD", key

down.

Location

400 401 402 403 404 405 406 407 410 411 412 413 414 415 416 417 420 421 422 423 424 425 426 427 430 431

176

Push "EXAM" key down (to sequentially examine each location).

The lower lights on the front of the PDP 8/e will indicate the

numbers which were entered.

The upper set of lights will indicate the location.

Light Numbers

bY ba

OOH

we

we “

ww

w

w

we

we

w

we

WKWWOREE

OOF

+»

» oOOF

HbHRe

fs PHP

QOrF

OOF

. bs

. bs

= ja

bs

bs

w

ww

w

Wo lo

GH WH

WO

WD WH

W& DW Ww

WH wD HW

&

©

WD WD Ww www

MEN MINN NNN NS

WO OWDWDMWMAMMDAWO

WOO OH RH

w

ww

w

w

w

we

Ne

w

w

ww

we

w

we

w

w

w

w

w

we

w

we

we

w

we

DOW wowowoworh

Fb

4

HA

. w

we

w.

‘

w

w

“se

we

When load is checked:

1.

2.

Enter 400 (Key 3 UP)

Previous Entry

1227 6731 6731 7600 6732 5204 6734 7106 7006 3232 6734 7012 7012 0226 1232 3631 2231 2230 5204 1203 6731 5014 0017 0401 7400 0000

Light Numbers

we “

WMmMeoOorMOrRPUU

Ps OW

Q-v

ww

we

w e

vy

“ iv)

v7

“ tv

) ‘e

»7,8,11

oO Pe

Wb

BPP

REFINE DERRY ERRYWOWN WEN

we

we

w pa fu

ww

ww

w ee

ee

eee

we

we we

ww

we

we el

OmlUlUlUOUlUlUlOlUlUlUOUlUlUlUOUlUlUUlUlUU

PONFENPE

NEAR

P NFP PRP NHR PHP

Bs

Rv

w w

« w

“ .

w vy

7 a

tv Y

‘ w

w “w

Ov vw

w w

FOODOONOFEFEHENFOOCOOFrCOCO

COCO CN

Press down "ADDR LOAD", "CLEAR", and "CONT".

Listing and Typing Files

A list of the file names contained on the upper disk are printed

by typing "DIR" on the active terminal. The information in each file

177

is typed by entering "TYPE File Name File Type”. Substituting "FLP:"

after each command, Dir or Type, will accomplish the same as that

above except the information will be generated form the lower disk.

Changing to Another Terminal

Either one of the two terminals (teletype or teleray’) can be

used with the PDP 8/e, at the discretion of the operator. During

the operation of the system, it may become necessary to change from

one terminal to another (i.e., to receive a hard copy - teletype) which

is the simple procedure listed below:

Type the following on operating terminal after dot appears:

R TLS (press return)

1. When computer halts, (PDP 8/e, "RUN" light goes off) change

terminal switches (see Fig. 57) for desired terminal.

2. Press continue.

3. Computer should print a dot on now active terminal.

PDP 8/e Programs

A. Position Program — POS.RL

This program enables the operator to conveniently position

the diffractometer at any 20, XxX, ®, or W setting.

Type on operating terminal after viewing dot:

R POS (press return)

The response from the computer will be a series of questions

which, when answered correctly, can position the instrument to any

+

Teleray is preferred because of its speed.

178

set point. The smallest movement in this program is 0.0025 degrees

which is one step of a motor. An example:

THE PROGRAM WILL NOW SLEW A MOTOR, INPUT MOTOR SELECT NUMBER: 1=2-THETA, 2=OMEGA, 3=CHL, 4-FI

1 IN WHICH DIRECTION DO YOU WISH TO GO:0=UP,1=DOWN. (UP-HIGHER ANGLE DOWN-LOWER ANGLE)

1 HOW MANY DEGREES DO YOU WISH TO MOVE? (F9.4)

100.0 DO YOU WANT TO SLEW AGAIN?: 1=YES,0=NO.

0 «

THE PROGRAM WILL NOT TAKE OUT BAKLASH 1=2-THETA, 2=OMEGA, 3=CHL, 4-FI

1 IN WHICH DIRECTION DO YOU WISH TO GO: O=UP,1=DOWN.

0 HOW MANY DEGREES DO YOU WISH TO MOVE? (F9.4)

1. DO YOU WANT TO TAKE OUT BAKLASH AGAIN: 1=YES, 0=NO

0

In this example, two theta was positioned 99° below its original

value prior to execution of data collection. It should be emphasized

that no data is collected with POS.RL.

B. Data Collection Programs

1. As in any of the following programs, POS.RL is available

as a separate program as given in "A" to the operator for positioning

the diffractometer. The program CH.RL is used with the usual chart

recorder operation while scanning either 20, xy, %, orw The program

is self-explanatory and is operated by typing the following on the

active terminal after viewing a dot:

R CH

The response from the computer will be a series of questions which

179

must be answered to initiate the scan. If a scanning speed of 1/32°/min

is desired the following should be typed on the active terminal instead

of that above:

R_CH32

2. A combination of a loading, running, and scaling program,

"Search" will quickly collect data over as many as nine different

regions. Scanning speeds of 5 or 1.25 degrees per min. along with

interrupt times of .1, .2, .3, and .4 min. yield a variable range of

detail which is then plotted by the teletype in the form of an

intensity bar graph. The optimum choice of speed and interrupt time

depends upon the c/m and is determined by experience. After viewing a

dot type:

R_Gl

The computer will now ask the appropriate question on the teleray

Screen so that the scanning program will be loaded. The load including

the data will be stored in a file called "KMAND2.DA". An example of

a load is given for a Chi scan:

.THIS PROGRAM SCANS SPECIFIC REGIONS FOR AVERAGE COUNTS, AND OUTPUTS THEM IN GRAPHIC FORM

FOR IDENTIFICATION, FILL IN THE INFORMATION BELOW THE * &

SPECIMEN MONTH DAY YEAR HRAKAKRKEAESH Ks ws RK

SAMPLE

TARGET VOLTAGE (KV) CURRENT (MA) MONOCHROMATOR wk* wk kk k4*

CU 50 20 C ENT. SLIT (DEG) REC. SLIT (DEG) KKK ReK

1.0 1.0

SCANNING SPEED (DEG/MIN) ARK

1.0 ON THE NEXT THREE LINES GIVE OTHER INFORMATION (20 CHARS./LINE)

180

DO YOU WISH TO SLEW A MOTOR?:1=YES,0=NO

0 DO YOU WISH TO TAKE OUT THE BACKLASH? :1=YES,0=NO

8)

IT IS NOW TIME TO COLLECT DATA ON THE CURVE 1=2-~THETA, 2=OMEGA, 3=CHI1, 4=FIL

3

INPUT SCAN SPEED:1=5,2=1.25 (DEG/MIN) 1 INPUT INTERRUPT RATE: 1=0.1, 2=0.2, 3=0.4 (MIN)

1 DO YOU WANT TO SPIN CHI: 1=YES,0=NO

0 HOW MANY PEAKS ARE TO BE SCANNED?

1 IN RESPONSE TO EACH QUESTION, INPUT LO, THEN HI ANGLE FOR EACH PEAK IN F9.4 FORMET. ? LO HI

00.00 90.00 0.0000 90.0000

INPUT PRESENT POSITION, FORMAT F9.4 0.00

To start data collection:

R G2

The run light on the front of the PDP 8/e will go out. The program

will start execution when the "continue" button is pressed down.

The program "GRAPH" will output the intensity bar graph on the

teletype and is run by typing the following;

R_GRAPH

The input needed for the graph program is the data file name and a

file name in which the graph is to be stored. If a second copy of the

output from the scan program is desired, type on the teleray/teletype

the following after viewing a dot:

R_READ

181

The input data file used for "READ" is "GRAPH1.DA".

3. Twenty different motor operations, each executing scans over

as many as nine different regions, can be accomplished by the following

pair of programs. Included in the output from RSCAN will be the

Integrated Intensity, Mean, and Variance without a correction for

background, see program "IMV" for the correction. Background points are

determined by the operator prior to the execution of IMV. To load this

program:

Type on operating terminal:

R_LSCAN

The response from the computer will be a series of questions which

will operate the 'RSCAN" program, for example:

THIS PROGRAM SCANS SPECIFIC REGIONS FOR AVERAGE COUNTS,

INTEGRATED INTENSITY, MEAN, AND AVERAGE VALUES.

DO YOU WISH TO SLEW A MOTOR?: 1=YES, O=NO 0 .

DO YOU WISH TO TAKE OUT THE BACKLASH?: 1=YES, O=NO

0

IT IS NOW TIME TO COLLECT DATA ON THE CURVE*

1=2-THETA, 2=2-OMEGA, 3=CHI, 4=PHI

3

INPUT SCAN SPEED: 1=1/5,2=1/10,3=1/20, 4=1/50,5=1/100,8=1 (DEG/MIN)

8 DO YOU WANT TO SPIN CHI: 1=YES,0=NO

0

HOW MANY PEAKS ARE TO BE SCANNED?

1

IN RESPONSE TO EACH QUESTION, INPUT LO, THEN HI ANGLE FOR

EACH PEAK IN F9.4 FORMAT.

LO HI

00.00 90.00

0.0000 90.0000

INPUT PRESENT POSITION, FORMAT F9.4

0.00

*the motor desired to operate

182

FOR IDENTIFICATION, FILL IN THE INFORMATION BELOW THE * 8

SPECIMEN MONTH DAY YEAR

Ke keRARKAS wAK *K* *w*

SAMPLE

TARGET VOLTAGE (KV) CURRENT (MA) MONOCHROMATOR

ws k* wx kx

CU 50 20 C

ENT. SLIT (DEG) REC. SLIT (DEG) KK* hike

1.0 1.0

SCANNING SPEED (DEGREE/MIN)

#AAKK

1.0

ON THE NEXT THREE LINES GIVE OTHER INFORMATION (20 CHARS. /LINE)

END OF IDENTIFICATION FIELD ANOTHER SET OF DATA?: 1=YES, O=NO

0

If an additional operation is to be made, a "1" should be typed instead

of the "0" in the last statement, which circles the program back to

the beginning. This load will collect data in the same manner as the

example Chi scan from the previous section. The data collection is

activated by typing on the operating terminal:

R_RSCAN

(Symbols between dotted lines will be typed by the computer).

1. Run light will go out on PDP 8/e

2. Press "Continue"

NOTE: Termination of a program at any point can be accomplished by

pressing down the halt switch on the front of PDP 8/e.

After the data collection is completed, the computer will return

a dot to the active terminal. A background correction can be made on

183

the integrated intensity, mean:and variance through the use of "IMV"

which again is a self-explanatory program. Type on the active

terminal

R_IMV

An input and output file along with the background points determined

by the operator are the only information required in this program.

Data Analysis

The IBM 370 has many distinctive advantages in analyzing the

data obtained from the automated diffractometer. A plot of experi-

mental data along with much faster printing rates are easily accessed

over the phone line. Connection to the IBM 370 is made by:

Part 1

1. Position button box on top of teleray as follows (left to

right)

A. I1st up position

B. 2nd middle position

C. 3rd down position

D. 4th middle position

2. Turn "VADIC" on (located in rear)

3. Dial "9" for an outside line

4. Dial 951-7020, a tone will be given when switching is complete

5. Lift "up" on white button on top, left of phone

6. IBM 370 will print on terminal "370 on line"

User I.D. Password

8.

9.

184

Press "Return"

When computer stops printing, press ''Return" again.

At this point the log-on has been completed. The data transfer to

the IBM 370 from the PDP 8/e requires:

Part 2

1.

2.

Place the data transfer disk in upper Sykes unit.

Re-positioning the switch box on top of teleray to the

operating position for PDP (middle two down, all others in

middle position)

Type on active terminal R IBM which requires an input and

output file name. This input will be used for "GAPHIT"

(see below in plotting).

Type on terminal:

| R TO 370

The computer will print "Enter name of file to be transferred"

Enter the file name and press return

Re-position switches on box at top of teleray as given in

Part 1, statement 1.

Press "Continue" on PDP 8/e

Computer's run light will go out after data transfer is

complete.

This procedure will copy all data in the given file to the IBM 370

permanently. Graphing of data is accomplished by:

A. Typing on terminal (switches in same position as for transfer)

"GRAPHIT file name file type A

185

NOTE: File name is name of file, file type is kind of information

(i.e. Data).

and the printing of a file:

B. Type on terminal (switches in same position as for transfer)

TYPOUT file name file type A

Editing Files

Information for editing a file on either the PDP 8/e or IBM 370

(35) or the VPI CMS User's Guide, can be found in the 0S/8 Handbook

respectively. Some useful commands are listed below:

1. PDP 8/e Editor

Command Format Meaning

R #R Read file

L #L List file

#NL List line N of file

#M, NL List lines M through N

C #NC Change line |

#M, NC Delete and insert following lines

D #ND Delete line

#M,ND | Delete lines M through N

S #S Search for character entered

E #E Close the output file

186

2. IBM 370 Editor

Command Meaning

TYP List line

TYP N List N Lines

N List next line

DO Down to next line

UP Up to line

C/QQ/ZZ Change characters QQ to ZZ

FILE Close output file

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VITA

The author was born on November 27, 1953 in York, Pennsylvania.

He received his elementary and secondary school education in York,

along with two years at York College of Pennsylvania majoring in

engineering.

In December of 1975 he finished the requirements for a Bachelor

of Science in Metallurgical Engineering from Virginia Polytechnic

Institute and State University. He worked on his master's degree

from the Fall of 1975 as a graduate research assistant for

Dr. Charles R. Houska. In July of 1977 he joined Bethlehem Steel

Corporation's Steelton Plant in the Steel Operations Department.

The author is a member of the American Society for Metals,

Alpha Sigma Mu, and Sigma Xi.

He married the former Robin Lou Kramer on June 28, 1975.

Frank Ew Dietrich

An X-Ray Study of the Behavior of

Titanium Films on Silicon Substrates

by

Frank E. Dietrich

(ABSTRACT)

The thin film reaction between silicon and titanium did differ

from the ordinary diffusion process in bulk samples at elevated

temperatures. The lower free energy monosilicide formed prior to

the disilicide in bulk standards and was also the dominant reaction

product at lower temperatures in films. Titanium thin films, 2.3

microns thick, sustained considerable mechanical deformation during

cooling from elevated temperatures. Line broadening, greater than

that obtained from cold worked filings of titanium at room temperature,

necessitated the use of computer simulation techniques to analyze the

diffracted intensity from the reacted structure.

The structure and space group of titanium disilicide was confirmed

along with a determination of both structure factor forms and accurate

lattice parameters. A range of compositions for the monosilicide of

titanium was observed along with the identification of visi, 0”? as

a high temperature compound. The identification of the inaccuracies

and omissions present in the ASTM powder diffraction card files should

resolve the confusion in the literature on the reaction between

titanium films and silicon.

The temperatures for formation of silicides in thin films was

found to be substantially lower than previously reported? , indicative

of the oxide free interface of the silicon substrates. The identifi-

cation of the reactant silicides, deposited at the grain boundaries

and as planar film at interfaces, establishes this study as the first

attempt to develop a quantitative model for silicide formation in

this transition metal system.

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