SURFACES: AN INTRODUCTION · Atoms or molecules are physisorbed into a porous structure (e.g., a...
34
1 SURFACES: AN INTRODUCTION 1.1 Historical Perspective 5 1.2 Surfaces and Interfaces: Classification of Properties 7 1.3 External Surfaces 20 1.3.1 Surface Concentration 20 1.3.1.1 Clusters and Small Particles 21 1.3.1.2 Thin Films 22 1.3.2 Internal Surfaces: Microporous Solids 23 1.4 Clean Surfaces 25 1.5 Interfaces 26 1.5.1 Adsorption 27 1.5.2 Thickness of Surface Layers 27 1.6 The Techniques of Surface Science 27 1.7 Summary and Concepts 29 1.8 Problems 29 References 30 1.1 HISTORICAL PERSPECTIVE Surface science in general and surface chemistry in particular have a long and distinguished history. The spontaneous spreading of oil on water was described in ancient times and was studied by Benjamin Franklin. A timeline of the historical development of surface chemistry since then is shown in Figure 1.1. The application of catalysis started in the early 1800s, with the discovery of the platinum (Pt)-surface-catalyzed reaction of H 2 and O 2 in 1823 by Dobereiner. He used this reaction in his “lighter” (i.e., a portable flame) source, of which he sold a large number. By 1835 [1], the discovery of heterogeneous catalysis was complete thanks to the studies of Kirchhoff, Davy, Henry, Philips, Faraday, and Berzelius. It was at about this time that the Daguerre process was introduced for photography. The study of tri- bology, or friction, also started around this time, coinciding with the industrial revolution, Introduction to Surface Chemistry and Catalysis, Second Edition. By Gabor A. Somorjai and Yimin Li Copyright # 2010 John Wiley & Sons, Inc. 5 COPYRIGHTED MATERIAL
Transcript of SURFACES: AN INTRODUCTION · Atoms or molecules are physisorbed into a porous structure (e.g., a...
1SURFACES: AN INTRODUCTION
1.1 Historical Perspective 5
1.2 Surfaces and Interfaces: Classification of Properties 7
1.3 External Surfaces 201.3.1 Surface Concentration 20
1.3.1.1 Clusters and Small Particles 211.3.1.2 Thin Films 22
1.3.2 Internal Surfaces: Microporous Solids 23
1.4 Clean Surfaces 25
1.5 Interfaces 261.5.1 Adsorption 271.5.2 Thickness of Surface Layers 27
1.6 The Techniques of Surface Science 27
1.7 Summary and Concepts 29
1.8 Problems 29References 30
1.1 HISTORICAL PERSPECTIVE
Surface science in general and surface chemistry in particular have a long and distinguishedhistory. The spontaneous spreading of oil on water was described in ancient times and wasstudied by Benjamin Franklin. A timeline of the historical development of surface chemistrysince then is shown in Figure 1.1. The application of catalysis started in the early 1800s, withthe discovery of the platinum (Pt)-surface-catalyzed reaction of H2 and O2 in 1823 byDobereiner. He used this reaction in his “lighter” (i.e., a portable flame) source, of whichhe sold a large number. By 1835 [1], the discovery of heterogeneous catalysis was completethanks to the studies of Kirchhoff, Davy, Henry, Philips, Faraday, and Berzelius. It was atabout this time that the Daguerre process was introduced for photography. The study of tri-bology, or friction, also started around this time, coinciding with the industrial revolution,
Introduction to Surface Chemistry and Catalysis, Second Edition. By Gabor A. Somorjai and Yimin LiCopyright # 2010 John Wiley & Sons, Inc.
5
COPYRIG
HTED M
ATERIAL
although some level of understanding of friction appears in the work of Leonardo da Vinci.Surface-catalyzed chemistry-based technologies first appeared in the period of 1860–1912,starting with the Deacon process (2HCl þ O2! H2O þ Cl2), SO2 oxidation to SO3
(Messel, 1875), the reaction of methane (CH4) with steam to produce CO and H2 (Mond,1888), ammonia (NH3) oxidation (Ostwald, 1901), ethylene (C2H4) hydrogenation(Sabatier, 1902), and NH3 synthesis (Haber, Mittasch, 1905–1912). Surface tensionmeasurements and recognition of equilibrium constraints on surface-chemical processesled to the development of the thermodynamics of surface phases by Gibbs (1877). The exist-ence of polyatomic or polymolecular aggregates that lack crystallinity and diffuse slowly(e.g., gelatine and albumin) was described in 1861 by Graham, who called these systems“colloids”. Polymolecular aggregates that exhibit internal structure were called “micelles”by Nageli, and stable metal colloids were prepared by Faraday. However, the colloid subfieldof surface chemistry gained prominence at the beginning of the 20th century with the rise ofthe paint industry and the preparation of artificial rubbers. Studies of light bulb filament life-times, high-surface-area gas absorbers in the gas mask, and gas-separation technologies inother forms, led to investigations of atomic and molecular adsorption (Langmuir, 1915).The properties of chemisorbed and physisorbed monolayers, adsorption isotherms, dissocia-tive adsorption, energy exchange, and sticking upon gas–surface collisions were studied.Studies of electrode surfaces in electrochemistry led to the detection of the surface spacecharge [2] (for a review of electrochemistry in the 19th century, see Ref. [3]). The surfacediffraction of electrons was discovered by Davisson and Germer (1927). Major academicand industrial laboratories focusing on surface studies have been formed in Germany(Haber, Polanyi, Farkas, Bonhoefer), the United Kingdom (Rideal, Roberts, Bowden), the
CatalysisElectrochemistryPhotographyTribology
Adsorption scienceElectron emission Surface charge and
electron transportMicroporous solids Monolayer scienceSurface magnetic propertiesSurface mechanical propertiesOptical surfacesPolymer and bio- polymer surfacesNanoparticle science
MACROSCOPIC MOLECULAR
1800 1850 1900 1950 2000 (Year)
Surface instrumentationSurface thermodynamicsColloids
Figure 1.1. Timeline of the historical development of surface chemistry.
6 SURFACES: AN INTRODUCTION
United States (Langmuir, Emmett, Harkins, Taylor, Ipatief, Adams), and many othercountries. They have helped to bring surface chemistry into the center of development ofchemistry—both because of the intellectual challenge to understand the rich diversity ofsurface phenomena and because of its importance in chemical and energy conversiontechnologies.
In the early 1950s, focus in chemistry research shifted to studies of gas-phase molecularprocesses, as many new techniques were developed to study gas-phase species on the mol-ecular level. This was not the case in surface and interface chemistry, although the newlydeveloped field-ion and electron microscopies did provide atomic level information on sur-face structure. The development of surface-chemistry-based technologies continued at a veryhigh rate, however, especially in areas of petroleum refining and the production of commod-ity chemicals. Then, in the late 1950s, the rise of the solid-state-device-based electronicsindustry and the availability of economical ultrahigh vacuum systems (UHV) (developedby research in space sciences) provided surface chemistry with new challenges and oppor-tunities, resulting in an explosive growth of the discipline. Clean surfaces of single crystalscould be studied for the first time, and the preparation of surfaces and interfaces with knownatomic structure and controlled composition was driving the development of microelec-tronics and computer technologies. New surface instrumentation and techniques havebeen developed that permit the study of surface properties on the atomic scale. Many ofthe most frequently used surface characterization techniques are listed in Table 1.1. Mostof these have been developed since the 1960s.
As a result of the sudden availability of surface characterization techniques, macroscopicsurface phenomena (adsorption, bonding, catalysis, oxidation and other surface reactions,diffusion, desorption, melting and other phase transformation, growth, nucleation, chargetransport, atom, ion, and electron scattering, friction, hardness, lubrication) are beingre-examined on the molecular scale. This finding has led to a remarkable growth of surfacechemistry that has continued uninterrupted to date. The discipline has again become oneof the frontier areas of chemistry. The newly gained knowledge of the molecular ingredientsof surface phenomena has given birth to a steady stream of high-technology products,including new hard coatings that passivate surfaces; chemically treated glass, semiconduc-tor, metal, and polymer surfaces, where the treatment imparts unique surface properties;newly designed catalysts, chemical sensors, and carbon fiber composites; surface-space-charge-based copying; and new methods of electric, magnetic, and optical signal processingand storage. Molecular surface chemistry is being utilized increasingly in biologicalscience.
1.2 SURFACES AND INTERFACES: CLASSIFICATION OF PROPERTIES
Condensed phases (solids and liquids) must have surfaces or interfaces. The suit of an astro-naut maneuvering in outer space represents a solid–vacuum interface (Fig. 1.2a); a basket-ball player jumping to score is a moving solid–gas interface (Fig. 1.2b); a sailboat movingover the waves is a solid–liquid interface (Fig. 1.2c); a tire sliding at the solid–solid interface(Fig. 1.2d). The surface of a lake is a liquid–gas interface. Olive oil poured on top of an openbottle of wine to prevent air oxidation forms a liquid–liquid interface. These interfaces exhi-bit some remarkable physical and chemical properties. The chemical behavior of surfaces isresponsible for heterogeneous catalysis (e.g., NH3 synthesis) and gas separations (as in theextraction of oxygen and nitrogen from air) by selective adsorption. Mechanical surface
1.2 SURFACES AND INTERFACES: CLASSIFICATION OF PROPERTIES 7
TA
BL
E1.
1Su
rfac
eSc
ienc
eT
echn
ique
s
Acr
onym
Nam
eD
escr
iptio
nP
rim
ary
Sur
face
Info
rmat
ion
Ads
orpt
ion
orse
lect
ive
chem
isor
ptio
ns[4
]A
tom
sor
mol
ecul
esar
eph
ysis
orbe
din
toa
poro
usst
ruct
ure
(e.g
.,a
zeol
iteor
asa
mpl
eof
coal
)or
onto
asu
rfac
e,an
dth
eam
ount
ofga
sad
sorb
edis
am
easu
reof
the
surf
ace
area
avai
labl
efo
rad
sorp
tion.
Che
mis
orpt
ion
ofat
oms
orm
olec
ules
onsu
rfac
esyi
elds
surf
ace
conc
entr
atio
nof
sele
cted
elem
ents
orad
sorp
tion
site
s.
Sur
face
area
,ads
orpt
ion
site
conc
entr
atio
n
AD
Ato
mor
heliu
mdi
ffra
ctio
n[5
–16]
Mon
oene
rget
icbe
ams
ofat
oms
are
scat
tere
dfr
omor
dere
dsu
rfac
esan
dde
tect
edas
afu
nctio
nof
scat
teri
ngan
gle.
Thi
sgi
ves
stru
ctur
alin
form
atio
non
the
oute
rmos
tla
yer
ofth
esu
rfac
e.A
tom
diff
ract
ion
isex
trem
ely
sens
itive
tosu
rfac
eor
deri
ngan
dde
fect
s.
Sur
face
stru
ctur
e
AE
AP
SA
uger
elec
tron
appe
aran
cepo
tent
ial
spec
tros
copy
[5–7
,17–
20]
Am
onoe
nerg
etic
beam
ofel
ectr
ons
isus
edto
exci
teat
oms
inth
ene
arsu
rfac
ere
gion
.As
the
beam
ener
gyis
swep
t,va
riat
ions
inth
esa
mpl
eem
issi
oncu
rren
tocc
uras
the
beam
ener
gysw
eeps
over
the
ener
gyof
anA
uger
tran
sitio
nin
the
sam
ple.
Als
okn
own
asA
PAE
S.
Che
mic
alco
mpo
sitio
n
AE
SA
uger
elec
tron
spec
tros
copy
[5–7
,17
,19,
21–3
2]C
ore-
hole
exci
tatio
nsar
ecr
eate
d,us
ually
by1
–10
-keV
inci
dent
elec
tron
s;A
uger
elec
tron
sof
char
acte
rist
icen
ergi
esar
eem
itted
thro
ugh
atw
o-el
ectr
onpr
oces
sas
exci
ted
atom
sde
cay
toth
eir
grou
ndst
ate.
AE
Sgi
ves
info
rmat
ion
onth
ene
ar-s
urfa
cech
emic
alco
mpo
sitio
n.
Che
mic
alco
mpo
sitio
n
AF
MA
tom
icfo
rce
mic
rosc
opy
[33–
40]
Ver
ysi
mila
rto
scan
ning
tunn
elin
gm
icro
scop
y(S
TM
).In
this
tech
niqu
e,ho
wev
er,t
heat
trac
tive
van
der
Waa
lsfo
rces
betw
een
the
surf
ace
and
the
prob
eca
use
abe
ndin
gof
the
prob
e.T
his
defl
ectio
nis
mea
sura
ble
bya
vari
ety
ofm
eans
.Bec
ause
this
tech
niqu
edo
esno
tre
quir
ea
curr
ent
betw
een
the
prob
ean
dth
esu
rfac
e,no
ncon
duct
ing
surf
aces
may
beim
aged
.
Sur
face
stru
ctur
e
APA
ES
App
eara
nce
pote
ntia
laug
erel
ectr
onsp
ectr
osco
pyS
eeA
EA
PS
.
8
AP
XP
SA
ppea
ranc
epo
tent
ial
X-r
ayph
otoe
mis
sion
spec
tros
copy
[5–7
,19
]
The
EA
PF
Sex
cita
tion
cros
sse
ctio
nis
mon
itore
dby
fluo
resc
ence
from
core
hole
deca
y(a
lso
know
nas
SX
AP
S).
Che
mic
alco
mpo
sitio
n
AR
AE
SA
ngle
-res
olve
dau
ger
elec
tron
spec
tros
copy
[41]
Aug
erel
ectr
ons
are
dete
cted
asa
func
tion
ofan
gle
topr
ovid
ein
form
atio
non
the
spat
ial
dist
ribu
tion
oren
viro
nmen
tof
the
exci
ted
atom
s(s
eeA
ES
).
Sur
face
stru
ctur
e
AR
PE
FS
Ang
le-r
esol
ved
phot
oem
issi
onex
tend
edfi
nest
ruct
ure
[41–
43]
Ele
ctro
nsar
ede
tect
edat
give
nan
gles
afte
rbe
ing
phot
oem
itted
bypo
lari
zed
sync
hrot
ron
radi
atio
n.T
hein
terf
eren
cein
the
dete
cted
phot
oem
issi
onin
tens
ityas
afu
nctio
nof
elec
tron
ener
gy�
100
–50
0eV
abov
eth
eex
cita
tion
thre
shol
dgi
ves
stru
ctur
alin
form
atio
n.
Sur
face
stru
ctur
e
AR
PE
SA
ngle
-res
olve
dph
otoe
mis
sion
spec
tros
copy
[6,2
7,44
–47]
Age
nera
lte
rmfo
rst
ruct
ure-
sens
itive
phot
oem
issi
onte
chni
ques
,in
clud
ing
AR
PE
FS
,AR
XP
S,
AR
UP
S,
and
AR
XP
D.
Ele
ctro
nic
stru
ctur
e,su
rfac
est
ruct
ure
AR
UP
SA
ngle
-res
olve
dul
trav
iole
tph
otoe
mis
sion
spec
tros
copy
[6,4
5,48
–51]
Ele
ctro
nsph
otoe
mitt
edfr
omth
eva
lenc
ean
dco
nduc
tion
band
sof
asu
rfac
ear
ede
tect
edas
afu
nctio
nof
angl
e.T
his
give
sin
form
atio
non
the
disp
ersi
onof
thes
eba
nds
(whi
chis
rela
ted
tosu
rfac
est
ruct
ure)
and
also
give
sst
ruct
ural
info
rmat
ion
from
the
diff
ract
ion
ofth
eem
itted
elec
tron
s.
Val
ence
band
stru
ctur
e,bo
ndin
g
AR
XP
DA
ngle
-res
olve
dX
-ray
phot
oele
ctro
ndi
ffra
ctio
n[6
,41,
42,5
2–54
]S
imila
rto
AR
XP
San
dA
RP
EFS
.The
angu
lar
vari
atio
nin
the
phot
oem
issi
onin
tens
ityis
mea
sure
dat
afi
xed
ener
gyab
ove
the
exci
tatio
nth
resh
old
topr
ovid
est
ruct
ural
info
rmat
ion.
Sur
face
stru
ctur
e
AR
XP
SA
ngle
-res
olve
dX
-ray
phot
oem
issi
onsp
ectr
osco
py[6
,41,
42,5
2,53
]
The
diff
ract
ion
ofel
ectr
ons
phot
oem
itted
from
core
leve
lsgi
ves
stru
ctur
alin
form
atio
non
the
surf
ace.
Sur
face
stru
ctur
e
CE
MC
onve
rsio
nel
ectr
onM
ossb
auer
spec
tros
copy
[7,5
5–58
]A
surf
ace-
sens
itive
vers
ion
ofM
ossb
auer
spec
tros
copy
.Lik
eM
ossb
auer
spec
tros
copy
,thi
ste
chni
que
islim
ited
toso
me
isot
opes
ofce
rtai
nm
etal
s.A
fter
anu
cleu
sis
exci
ted
byg
-ray
abso
rptio
n,it
can
unde
rgo
inve
rseb
-dec
ay,c
reat
ing
aco
reho
le.
The
deca
yof
core
hole
sby
Aug
erpr
oces
ses
with
inan
elec
tron
mea
nfr
eepa
thof
the
surf
ace
prod
uces
asi
gnal
.Det
ectin
gem
itted
elec
tron
sas
afu
nctio
nof
ener
gygi
ves
som
ede
pth
profi
lein
form
atio
nbe
caus
eth
ech
angi
ngel
ectr
onm
ean
free
path
.
Che
mic
alen
viro
nmen
t,ox
idat
ion
stat
e
(Con
tinue
d)
9
TA
BL
E1.
1C
ontin
ued
Acr
onym
Nam
eD
escr
iptio
nP
rim
ary
Sur
face
Info
rmat
ion
DA
PS
Dis
appe
aran
cepo
tent
ial
spec
tros
copy
[5–7
,19]
The
EA
PF
Scr
oss
sect
ion
ism
onito
red
byva
riat
ions
inth
ein
tens
ityof
elec
tron
sba
ck-s
catte
red
from
the
surf
ace.
Che
mic
alco
mpo
sitio
n
EA
PF
SE
lect
ron
appe
aran
cepo
tent
ial
fine
stru
ctur
e[6
,59]
Afi
ne-s
truc
ture
tech
niqu
e(s
eeE
XA
FS
).C
ore
hole
sar
eex
cite
dby
mon
oene
rget
icel
ectr
ons.
The
mod
ulat
ion
inth
eex
cita
tion
cros
sse
ctio
nas
the
beam
ener
gyis
vari
edm
aybe
mon
itore
dth
roug
hab
sorp
tion,
fluo
resc
ence
,or
Aug
erem
issi
on.
Sur
face
stru
ctur
e
EL
NE
SE
lect
ron
ener
gylo
ssne
ared
gest
ruct
ure
Sim
ilar
toN
EX
AF
S,
exce
ptm
onoe
nerg
etic
high
-ene
rgy
elec
tron
s�
60–
300
keV
exci
teco
reho
les.
Sur
face
stru
ctur
e
EL
Sor
EE
LS
Ele
ctro
nen
ergy
loss
spec
tros
copy
[6,7
,23
,26,
44,6
0–63
]M
onoe
nerg
etic
elec
tron
sar
esc
atte
red
off
asu
rfac
e,an
dth
een
ergy
loss
esar
ede
term
ined
.T
his
give
sin
form
atio
non
the
elec
tron
icex
cita
tions
ofth
esu
rfac
ean
dth
ead
sorb
edm
olec
ules
.
Ele
ctro
nic
stru
ctur
e,su
rfac
est
ruct
ure
ES
CA
Ele
ctro
nsp
ectr
osco
pyfo
rch
emic
alan
alys
is[5
–7,
19,2
5,64
–66]
Now
gene
rally
calle
dX
PS
.C
ompo
sitio
n,ox
idat
ion
stat
e
ES
DIA
Dor
PS
DE
lect
ron
(pho
ton)
-stim
ulat
edio
nan
gula
rdi
stri
butio
n[5
–7,
11,6
7–72
]
Ele
ctro
nsor
phot
ons
brea
kch
emic
albo
nds
inab
sorb
edat
oms
orm
olec
ules
,ca
usin
gio
nize
dat
oms
orra
dica
lsto
beej
ecte
dfr
omth
esu
rfac
eal
ong
the
axis
ofth
ebr
oken
bond
byC
oulo
mb
repu
lsio
n.T
hean
gula
rdis
trib
utio
nof
thes
eio
nsgi
ves
info
rmat
ion
onth
ebo
ndin
gge
omet
ryof
adso
rbed
mol
ecul
es.
Bon
ding
geom
etry
,m
olec
ular
orie
ntat
ion
Elli
psom
etry
[73]
Use
dto
dete
rmin
eth
ickn
ess
ofan
adso
rbed
film
.Aci
rcul
arpo
lari
zed
beam
oflig
htis
refl
ecte
dfr
oma
surf
ace,
and
the
chan
gein
the
pola
riza
tion
char
acte
rist
ics
ofth
elig
htgi
ves
info
rmat
ion
abou
tth
esu
rfac
efi
lm.
Lay
erth
ickn
ess
EX
AF
SE
xten
ded
X-r
ayab
sorp
tion
fine
stru
ctur
e[6
,11,
74–8
0]M
onoe
nerg
etic
phot
ons
exci
tea
core
hole
.The
mod
ulat
ion
ofth
eab
sorp
tion
cros
sse
ctio
nw
ithen
ergy
at10
0–
500
eVab
ove
the
exci
tatio
nth
resh
old
yiel
dsin
form
atio
non
the
radi
aldi
stan
ces
toth
ene
ighb
orin
gat
oms.
The
cros
sse
ctio
nca
nbe
mea
sure
dby
fluo
resc
ence
asth
eco
reho
les
deca
yor
byat
tenu
atio
nof
the
tran
smitt
edph
oton
beam
.EX
AF
Sis
one
ofth
em
any
“fine
-str
uctu
re”
tech
niqu
es.
Loc
alsu
rfac
est
ruct
ure
and
coor
dina
tion
num
bers
10
EX
EL
FS
Ext
ende
dX
-ray
ener
gylo
ssfi
nest
ruct
ure
[6]
Mon
oene
rget
icel
ectr
ons
exci
tea
core
hole
.T
hem
odul
atio
nof
the
abso
rptio
ncr
oss
sect
ion
with
ener
gy10
0–
500
eVab
ove
the
exci
tatio
nth
resh
old
yiel
dsin
form
atio
non
the
radi
aldi
stan
ces
toth
ene
ighb
orin
gat
oms.
The
cros
sse
ctio
nca
nbe
mea
sure
dby
fluo
resc
ence
asth
eco
reho
les
deca
yor
byat
tenu
atio
nof
the
tran
smitt
edph
oton
beam
.
Loc
alsu
rfac
est
ruct
ure
and
coor
dina
tion
num
bers
FE
MF
ield
emis
sion
mic
rosc
opy
[5–7
,14
,23,
25,8
1,82
]A
stro
ngel
ectr
icfi
eld
(on
the
orde
rof
V/A
)is
appl
ied
toth
elip
ofa
shar
p,si
ngle
-cry
stal
wir
e.T
heel
ectr
ons
tunn
elin
toth
eva
cuum
and
are
acce
lera
ted
alon
gra
dial
traj
ecto
ries
byC
oulo
mb
repu
lsio
n.W
hen
the
elec
tron
sim
ping
eon
afl
uore
scen
tsc
reen
,va
riat
ions
ofth
eel
ectr
icfi
eld
stre
ngth
acro
ssth
esu
rfac
eof
the
tipar
edi
spla
yed.
Sur
face
stru
ctur
e
FIM
Fie
ldio
niza
tion
mic
rosc
opy
[5–7
,14
,23,
25,8
2,83
]A
stro
ngel
ectr
icfi
eld
(on
the
orde
rof
V/A
)is
crea
ted
atth
etip
ofa
shar
p,si
ngle
-cry
stal
wir
e.G
asat
oms,
usua
llyH
e,ar
epo
lari
zed
and
attr
acte
dto
the
tipby
the
stro
ngel
ectr
icfi
eld,
and
are
ioni
zed
byel
ectr
ons
tunn
elin
gfr
omth
ega
sat
oms
into
the
tip.T
hese
ions
,ac
cele
rate
dal
ong
radi
altr
ajec
tori
esby
Cou
lom
bre
puls
ion,
map
out
the
vari
atio
nsin
the
elec
tric
fiel
dst
reng
thac
ross
the
surf
ace,
show
ing
the
surf
ace
topo
grap
hyw
ithat
omic
reso
lutio
n.
Sur
face
stru
ctur
ean
dsu
rfac
edi
ffus
ion
FT
IRFo
urie
rtr
ansf
orm
infr
ared
spec
tros
copy
[84–
86]
Bro
ad-b
and
IRA
Sex
peri
men
tsar
epe
rfor
med
and
the
IRad
sorp
tion
spec
trum
isde
conv
olut
edus
ing
aD
oppl
er-s
hift
edso
urce
and
the
Four
ier
anal
ysis
ofth
eda
ta.
Thi
ste
chni
que
isno
tre
stri
cted
tosu
rfac
es.
Bon
ding
geom
etry
and
stre
ngth
HE
ISH
igh-
ener
gyio
nsc
atte
ring
spec
tros
copy
[6,1
4,87
,88]
Hig
h-en
ergy
ions
,abo
ve�
500
keV
,are
scat
tere
dof
fasi
ngle
-cry
stal
surf
ace.
The
“cha
nnel
ing”
and
“blo
ckin
g”of
scat
tere
dio
nsw
ithin
the
crys
tal
can
beus
edto
tria
ngul
ate
devi
atio
nsfr
omth
ebu
lkst
ruct
ure.
HE
ISha
sbe
enes
peci
ally
used
tost
udy
surf
ace
reco
nstr
uctio
nsan
dth
eth
erm
alvi
brat
ions
ofsu
rfac
eat
oms.
(See
also
ME
ISan
dIS
S.)
Sur
face
stru
ctur
e
HP
XP
SH
igh-
pres
sure
X-r
ayph
otoe
lect
ron
spec
tros
copy
[89,
90]
XP
Sfo
rin
situ
stud
yun
der
pres
sure
sup
to10
Tor
r.C
ompo
sitio
n,ox
idat
ion
stat
e
(Con
tinue
d)
11
TA
BL
E1.
1C
ontin
ued
Acr
onym
Nam
eD
escr
iptio
nP
rim
ary
Sur
face
Info
rmat
ion
HR
EE
LS
Hig
h-re
solu
tion
elec
tron
ener
gylo
sssp
ectr
osco
py[5
,6,9
1–93
]A
mon
oene
rget
icel
ectr
onbe
am,�
2–
10eV
,is
scat
tere
dof
fa
surf
ace;
and
the
ener
gylo
sses
betw
een�
0.5
eVto
bulk
and
surf
ace
phon
ons
and
vibr
atio
nal
exci
tatio
nsof
adso
rbat
esar
em
easu
red
asa
func
tion
ofan
gle
and
ener
gy(a
lso
calle
dE
EL
S).
Bon
ding
geom
etry
,su
rfac
eat
omvi
brat
ions
INS
Ion-
neut
raliz
atio
nsp
ectr
osco
py[5
,6,
94]
Slo
wio
nize
dat
oms,
usua
llyH
eþ,
stri
kea
surf
ace,
whe
reth
eyar
ene
utra
lized
ina
two-
elec
tron
proc
ess
that
can
ejec
ta
surf
ace
elec
tron
(apr
oces
ssi
mila
rto
Aug
erem
issi
onfr
omth
eva
lenc
eba
nd).
The
ejec
ted
elec
tron
sar
ede
tect
edas
afu
nctio
nof
ener
gy,
and
the
surf
ace
dens
ityof
stat
esca
nbe
dete
rmin
edfr
omth
een
ergy
dist
ribu
tion.
The
inte
rpre
tatio
nis
mor
eco
mpl
icat
edth
anfo
rS
PI
orU
PS
.
Val
ence
band
s
IPIn
vers
eph
oto-
emis
sion
[95–
100]
The
abso
rptio
nof
elec
tron
sby
asu
rfac
eis
mea
sure
das
afu
nctio
nof
ener
gyan
dan
gle.
Thi
ste
chni
que
give
sin
form
atio
nab
out
cond
uctio
nba
nds
and
unoc
cupi
edle
vels
.
Ele
ctro
nic
stru
ctur
e
IRA
SIn
frar
edre
flec
tion
adso
rptio
nsp
ectr
osco
py[6
,62,
63,8
6,10
1,10
2]
The
vibr
atio
nal
mod
esof
adso
rbed
mol
ecul
eson
asu
rfac
ear
est
udie
dby
mon
itori
ngth
eab
sorb
tion
orem
issi
onof
IRra
diat
ion
from
ther
mal
lyex
cite
dm
odes
asa
func
tion
ofen
ergy
.
Mol
ecul
arst
ruct
ure
ISS
Ion
scat
teri
ngsp
ectr
osco
py[5
–7,
11,1
03,
104]
Ions
are
scat
tere
dfr
oma
surf
ace,
and
the
chem
ical
com
posi
tion
ofth
esu
rfac
em
aybe
dete
rmin
edby
the
mom
entu
mtr
ansf
erto
surf
ace
atom
s.T
heen
ergy
rang
eis�
1ke
Vto
10M
eV,a
ndth
elo
wer
ener
gies
are
mor
esu
rfac
ese
nsiti
ve.A
thig
her
ener
gies
,thi
ste
chni
que
isal
sokn
own
asR
uthe
rfor
dba
ck-s
catte
ring
(RB
S).
Aco
mpi
latio
nof
surf
ace
stru
ctur
esde
term
ined
with
ion
scat
teri
ngsu
mm
ariz
ing
the
pre-
1988
liter
atur
eap
pear
sin
Ref
.[10
5].
Sur
face
stru
ctur
e,co
mpo
sitio
n
12
LE
ED
Low
-ene
rgy
elec
tron
diff
ract
ion
[5–7
,11
,13
–15,
23,
25,
26,
106–
109]
Mon
oene
rget
icel
ectr
ons
belo
w�
500
eVar
eel
astic
ally
back
-sc
atte
red
from
asu
rfac
ean
dde
tect
edas
afu
nctio
nof
ener
gyan
dan
gle.
Thi
sgi
ves
info
rmat
ion
onth
est
ruct
ure
ofth
ene
ar-s
urfa
cere
gion
.A
com
pila
tion
ofsu
rfac
est
ruct
ures
sum
mar
izin
gth
epr
e-19
86lit
erat
ure
appe
ars
inR
ef.[
110]
.
Sur
face
stru
ctur
e
LE
ISL
ow-e
nerg
yio
nsc
atte
ring
[6,7
,14,
111,
112]
Low
-ene
rgy
ions
belo
w�
5eV
are
scat
tere
dfr
oma
surf
ace,
and
the
ion
“sha
dow
ing”
give
sin
form
atio
non
the
surf
ace
stru
ctur
e.A
tth
ese
low
ener
gies
the
surf
ace-
atom
ion-
scat
teri
ngcr
oss
sect
ion
isve
ryla
rge,
resu
lting
inla
rge
surf
ace
sens
itivi
ty.A
ccur
acy
islim
ited
beca
use
the
low
-ene
rgy
ion-
scat
teri
ngcr
oss
sect
ions
are
not
wel
lkn
own.
Sur
face
stru
ctur
e
LE
PD
Low
-ene
rgy
posi
tron
diff
ract
ion
[113
,11
4]S
imila
rto
LE
ED
with
posi
tron
sas
the
inci
dent
part
icle
.The
inte
ract
ion
pote
ntia
lis
som
ewha
tdi
ffer
ent
than
for
elec
tron
s,so
the
form
ofth
est
ruct
ural
info
rmat
ion
ism
odifi
ed.
Sur
face
stru
ctur
e
ME
ED
Med
ium
-ene
rgy
elec
tron
diff
ract
ion
[14]
Sim
ilar
toL
EE
D,e
xcep
tth
een
ergy
rang
eis
high
er,
�30
0–
1000
eV.
Sur
face
stru
ctur
e
ME
ISM
ediu
m-e
nerg
yio
nsc
atte
ring
[7,1
4]S
imila
rto
HE
IS,e
xcep
tth
atin
cide
ntio
nen
ergi
esar
e�
50–
500
keV
.S
urfa
cest
ruct
ure
Neu
tron
diff
ract
ion
[115
–117
]N
eutr
ondi
ffra
ctio
nis
not
anex
plic
itly
surf
ace
sens
itive
tech
niqu
e,bu
tneu
tron
diff
ract
ion
expe
rim
ents
onla
rge-
surf
ace-
area
sam
ples
have
prov
ided
impo
rtan
tst
ruct
ural
info
rmat
ion
onad
sorb
edm
olec
ules
and
also
onsu
rfac
eph
ase
tran
sitio
ns.
Sur
face
stru
ctur
e
NE
XA
FS
Nea
r-ed
geX
-ray
abso
rptio
nlin
est
ruct
ure
[74,
75,1
18–1
20]
Aco
reho
leis
exci
ted
asin
fine
-str
uctu
rete
chni
ques
(see
EX
AF
S,
SE
XA
FS
.AR
-PE
FS
.NP
D.A
PD
,EX
EL
FS
,SE
EL
FS)e
xcep
ttha
tth
efi
nest
ruct
ure
with
in�
30eV
ofth
eex
cita
tion
thre
shol
dis
mea
sure
d.M
ultip
lesc
atte
ring
ism
uch
stro
nger
atlo
wel
ectr
onen
ergi
es,
soth
iste
chni
que
isse
nsiti
veto
the
loca
l3D
geom
etry
,no
tju
stth
era
dial
sepa
ratio
nbe
twee
nth
eso
urce
atom
and
itsne
ighb
ors.
The
exci
tatio
ncr
oss
sect
ion
may
bem
onito
red
byde
tect
ing
the
phot
oem
itted
elec
tron
sor
the
Aug
erel
ectr
ons
emitt
eddu
ring
the
core
-hol
ede
cay.
Sur
face
stru
ctur
e
(Con
tinue
d)
13
TA
BL
E1.
1C
ontin
ued
Acr
onym
Nam
eD
escr
iptio
nP
rim
ary
Sur
face
Info
rmat
ion
NM
RN
ucle
arm
agne
ticre
sona
nce
[121
,12
2]N
MR
isno
tan
expl
icitl
ysu
rfac
e-se
nsiti
vete
chni
que,
butN
MR
data
onla
rge
surf
ace
area
sam
ples
(�1
m2)
have
prov
ided
usef
ulda
taon
mol
ecul
arad
sorp
tion
geom
etri
es.
The
nucl
eus
mag
netic
mom
ent
inte
ract
sw
ithan
exte
rnal
lyap
plie
dm
agne
ticfi
eld
and
prov
ides
spec
tra
high
lyde
pend
ent
onth
enu
clea
ren
viro
nmen
tof
the
sam
ple.
The
sign
alin
tens
ityis
dire
ctly
prop
ortio
nal
toth
eco
ncen
trat
ion
ofth
eac
tive
spec
ies.
Thi
sm
etho
dis
limite
dto
the
anal
ysis
ofm
agne
tical
lyac
tive
nucl
ei.
Che
mic
alst
ate
NP
DN
orm
alph
otoe
lect
ron
diff
ract
ion
[41,
42]
Sim
ilar
toA
RP
EF
S,b
utw
itha
som
ewha
tlo
wer
ener
gyra
nge.
Sur
face
stru
ctur
e
PM
-RA
IRS
Pola
riza
tion-
mod
ulat
edre
flet
ion-
abso
rptio
nin
frar
edsp
ectr
osco
py[1
23–1
25]
An
refle
ctio
n–
abso
rptio
nIR
spec
tros
copy
that
utili
zes
the
IRse
lect
ion
rule
onm
etal
surf
aces
toac
hiev
eth
esu
rfac
ese
nsiti
vity
.M
olec
ular
stru
ctur
e,su
rfac
ere
actio
nin
term
edia
tes
RB
SR
uthe
rfor
dba
ck-s
catte
ring
[5,6
,12
6,12
7]S
imila
rto
ISS
,exc
ept
that
the
mai
nfo
cus
ison
dept
h-pr
ofilin
gan
dco
mpo
sitio
n.T
hem
omen
tum
tran
sfer
inba
ck-s
catte
ring
colli
sion
sbe
twee
nnu
clei
isus
edto
iden
tify
the
nucl
ear
mas
ses
inth
esa
mpl
e,an
dth
esm
alle
r,gr
adua
lm
omen
tum
loss
ofth
ein
cide
ntnu
cleu
sth
roug
hel
ectr
on–
nucl
eus
inte
ract
ions
prov
ides
dept
h-pr
ofile
info
rmat
ion.
Com
posi
tion
RH
EE
DR
eflec
tion
high
-ene
rgy
elec
tron
diff
ract
ion
[6,7
,13,
14,2
5,12
8]M
onoe
nerg
etic
elec
tron
sbe
low�
1–
20ke
Var
eel
astic
ally
scat
tere
dfr
oma
surf
ace
atgl
anci
ngin
cide
nce,
and
dete
cted
asa
func
tion
ofen
ergy
and
angl
efo
rsm
all
forw
ard-
scat
teri
ngan
gles
.Bac
k-sc
atte
ring
isle
ssim
port
ant
athi
ghen
ergi
es,a
ndgl
anci
ngin
cide
nce
isus
edto
enha
nce
surf
ace
sens
itivi
ty.
Sur
face
stru
ctur
e.st
ruct
ure
ofth
infi
lms
SE
EL
FS
Sur
face
elec
tron
ener
gylo
ssfi
nest
ruct
ure
[80,
129,
130]
Afi
ne-s
truc
ture
tech
niqu
esi
mila
rto
EX
EL
FS
,exc
ept
the
inci
dent
elec
tron
ism
ore
surf
ace
sens
itive
beca
use
ofth
elo
wer
exci
tatio
nen
ergy
.Aco
mpi
latio
nof
surf
ace
stru
ctur
esde
term
ined
usin
gS
EE
LF
San
dS
EX
AF
Ssu
mm
ariz
ing
the
pre-
1990
liter
atur
eap
pear
sin
Ref
.[13
1].
Sur
face
stru
ctur
e
14
SE
RS
Sur
face
enha
nced
Ram
ansp
ectr
osco
py[6
2,13
2,13
3]S
ome
surf
ace
geom
etri
es(r
ough
surf
aces
)co
ncen
trat
eth
eel
ectr
icfi
elds
ofR
aman
scat
teri
ngcr
oss
sect
ion
soth
atit
issu
rfac
ese
nsiti
ve.
Thi
sgi
ves
info
rmat
ion
onsu
rfac
evi
brat
iona
lm
odes
,an
dso
me
info
rmat
ion
onge
omet
ryvi
ase
lect
ion
rule
s.
Sur
face
stru
ctur
e
SE
XA
FS
Sur
face
exte
nded
X-r
ayab
sorp
tion
fine
stru
ctur
e[6
,11,
75,1
29,
134–
136]
Am
ore
surf
ace-
sens
itive
vers
ion
ofE
XA
FS
,w
here
the
exci
tatio
ncr
oss-
sect
ion
fine
stru
ctur
eis
mon
itore
dby
dete
ctin
gth
eph
otoe
mitt
edel
ectr
ons
(PE
–S
EX
–A
FS
),A
uger
elec
tron
sem
itted
duri
ngco
re-h
ole
deca
y(A
uger
–S
EX
AF
S),
orio
nsex
cite
dby
phot
oele
ctro
nsan
dde
sorb
edfr
omth
esu
rfac
e(P
SD
–S
EX
–A
FS
).A
com
pila
tion
ofsu
rfac
est
ruct
ures
dete
rmin
edus
ing
SE
EL
FSan
dS
EX
AF
Ssu
mm
ariz
ing
the
pre-
1990
liter
atur
eap
pear
sin
Ref
.[13
1].
Sur
face
stru
ctur
e
SFA
Sur
face
forc
eap
para
tus
[137
–140
]T
wo
bent
mic
ash
eets
with
atom
ical
lysm
ooth
surf
aces
are
brou
ght
toge
ther
with
dist
ance
ofse
para
tion
inth
ena
nom
eter
rang
e.T
hefo
rces
actin
gon
mol
ecul
arla
yers
betw
een
the
mic
apl
ates
perp
endi
cula
ran
dpa
ralle
lto
the
plat
esu
rfac
esca
nbe
mea
sure
d.
Forc
esac
ting
onm
olec
ules
sque
ezed
betw
een
mic
apl
ates
are
mea
sure
d.
SFG
Sum
freq
uenc
yge
nera
tion
[141
–143
]S
imila
rm
SH
G.O
neof
the
lase
rsha
sa
tuna
ble
freq
uenc
yth
atpe
rmits
vari
atio
nof
the
seco
ndha
rmon
icsi
gnal
.In
this
way
,the
vibr
atio
nal
exci
tatio
nof
the
adso
rbed
mol
ecul
esis
achi
eved
.
Sur
face
stru
ctur
e
SH
GS
econ
dha
rmon
icge
nera
tion
[141
,14
4,14
5]A
surf
ace
isill
umin
ated
with
ahi
gh-i
nten
sity
lase
r,an
dph
oton
sar
ege
nera
ted
atth
ese
cond
harm
onic
freq
uenc
yth
roug
hno
nlin
ear
optic
alpr
oces
ses.
For
man
ym
ater
ials
,onl
yth
esu
rfac
ere
gion
has
the
appr
opri
ate
sym
met
ryto
prod
uce
the
SH
Gsi
gnal
.T
heno
nlin
ear
pola
riza
bilit
yte
nsor
depe
nds
onth
ena
ture
and
geom
etry
ofad
sorb
edat
oms
and
mol
ecul
es.
Ele
ctro
nic
stru
ctur
e,m
olec
ular
orie
ntat
ion
SIM
SS
econ
dary
ion
mas
ssp
ectr
omet
ry[5
–7,
104,
146–
152]
Ions
and
ioni
zed
clus
ters
ejec
ted
from
asu
rfac
edu
ring
ion
bom
bard
men
tar
ede
tect
edw
itha
mas
ssp
ectr
omet
er.
Sur
face
chem
ical
com
posi
tion
and
som
ein
form
atio
non
bond
ing
can
beex
trac
ted
from
SIM
Sio
nfr
agm
ent
dist
ribu
tions
.
Sur
face
com
posi
tion (C
ontin
ued
)
15
TA
BL
E1.
1C
ontin
ued
Acr
onym
Nam
eD
escr
iptio
nP
rim
ary
Sur
face
Info
rmat
ion
SP
IS
urfa
cepe
nnin
gio
niza
tion
[5,2
6]N
eutr
alat
oms,
usua
llyH
e,in
elec
tron
ical
lyex
cite
dst
ates
colli
dew
itha
surf
ace
atth
erm
alen
ergi
es.A
surf
ace
elec
tron
may
tunn
elin
toan
unoc
cupi
edel
ectr
onic
leve
lof
the
inco
min
gga
sat
om,
caus
ing
the
inci
dent
atom
toio
nize
and
ejec
tan
elec
tron
,whi
chis
then
dete
cted
.Thi
ste
chni
que
mea
sure
sth
ede
nsity
ofst
ates
near
the
Ferm
ile
vel
ofth
esu
bstr
ate
and
ishi
ghly
surf
ace
sens
itive
.
Ele
ctro
nic
stru
ctur
e
SP
LE
ED
Spi
n-po
lari
zed
low
-ene
rgy
elec
tron
diff
ract
ion
[27,
153]
Sim
ilar
toL
EE
D,e
xcep
tth
ein
cide
ntel
ectr
onbe
amis
spin
pola
rize
d.T
his
fact
ispa
rtic
ular
lyus
eful
for
the
stud
yof
surf
ace
mag
netis
man
dm
agne
ticor
deri
ng.
Mag
netic
stru
ctur
e
ST
MS
cann
ing
tunn
elin
gm
icro
scop
y[5
,38,
154–
160]
The
topo
grap
hyof
asu
rfac
eis
mea
sure
dby
mec
hani
cally
scan
ning
ofa
prob
eov
era
surf
ace.
The
dist
ance
from
the
prob
eto
the
surf
ace
ism
easu
red
byth
epr
obe-
surf
ace
tunn
elin
gcu
rren
t.A
ngst
rom
reso
lutio
nof
surf
ace
feat
ures
isro
utin
ely
obta
ined
.
Sur
face
stru
ctur
e
SX
AP
SS
oft
X-r
ayap
pear
ance
pote
ntia
lsp
ectr
osco
pyA
noth
erna
me
for
AP
XP
S.
TE
MT
rans
mis
sion
elec
tron
mic
rosc
opy
[14,
15,1
61,1
62]
TE
Mca
npr
ovid
esu
rfac
ein
form
atio
nfo
rca
refu
llypr
epar
edan
dor
ient
edbu
lksa
mpl
es.R
eali
mag
esha
vebe
enfo
rmed
ofth
eed
ges
ofcr
ysta
lsw
here
surf
ace
plan
esan
dsu
rfac
edi
ffus
ions
have
been
obse
rved
.Dif
frac
tion
patte
rns
ofre
cons
truc
ted
surf
aces
,su
peri
mpo
sed
onth
ebu
lkdi
ffra
ctio
npa
ttern
,ha
veal
sopr
ovid
edsu
rfac
est
ruct
ural
info
rmat
ion.
Sur
face
stru
ctur
e
TD
ST
herm
alde
sorp
tion
spec
tros
copy
[6,1
63–1
67]
An
adso
rbat
e-co
vere
dsu
rfac
eis
heat
ed,u
sual
lyat
alin
ear
rate
,and
the
deso
rbin
gat
oms
orm
olec
ules
are
dete
cted
with
am
ass
spec
trom
eter
.T
his
give
sin
form
atio
non
the
natu
reof
adso
rbat
esp
ecie
san
dso
me
info
rmat
ion
onad
sorp
tion
ener
gies
and
the
surf
ace
stru
ctur
e.
Com
posi
tion,
heat
ofad
sorp
tion,
surf
ace
stru
ctur
e
16
TD
PT
empe
ratu
repr
ogra
mm
edde
sorp
tion
[6,1
65–1
67]
Sim
ilar
toT
DS
,exc
ept
the
surf
ace
may
behe
ated
ata
nonu
nifo
rmra
teto
obta
inm
ore
sele
ctiv
ein
form
atio
non
adso
rptio
nen
ergi
es.
Com
posi
tion,
heat
ofad
sorp
tion,
surf
ace
stru
ctur
eU
PS
Ultr
avio
let
phot
oem
issi
onsp
ectr
osco
py[5
–7,2
3,25
,26,
45,
94,1
68,
169]
Ele
ctro
nsph
otoe
mitt
edfr
omth
eva
lenc
ean
dco
nduc
tion
band
sar
ede
tect
edas
afu
nctio
nof
ener
gyto
mea
sure
the
elec
tron
icde
nsity
ofst
ates
near
the
surf
ace.
Thi
sgi
ves
info
rmat
ion
onth
ebo
ndin
gof
adso
rbat
esto
the
surf
ace
(see
AR
UP
S).
Val
ence
band
stru
ctur
e
Wor
kfu
nctio
nm
easu
rem
ents
[6,2
3,25
,170
,171
]C
hang
esin
asu
bstr
ate’
sw
ork
func
tion
duri
ngth
ead
sorp
tion
ofat
oms
and
mol
ecul
espr
ovid
ein
form
atio
nab
out
char
getr
ansf
erbe
twee
nth
ead
sorb
ate
and
the
subs
trat
ean
dal
soab
out
chem
ical
bond
ing.
Ele
ctro
nic
stru
ctur
e
XA
NE
SX
-ray
abso
rbtio
nne
ar-e
dge
stru
ctur
eA
noth
erna
me
for
NE
XA
FS
.
XP
SX
-ray
phot
oem
issi
onsp
ectr
osco
py[5
,7,
12,6
4–66
,172
,173
]E
lect
rons
phot
oem
itted
from
atom
icco
rele
vels
are
dete
cted
asa
func
tion
ofen
ergy
.The
shif
tsof
core
-lev
elen
ergi
esgi
vein
form
atio
non
the
chem
ical
envi
ronm
ent
ofth
eat
oms
(see
AR
XP
S,
AR
XP
D).
Com
posi
tion,
oxid
atio
nst
ate
XR
DX
-ray
diff
ract
ion
[174
–176
]X
-ray
diff
ract
ion
has
been
carr
ied
outa
text
rem
egl
anci
ngan
gles
ofin
cide
nce
whe
reto
tal
refl
ectio
nen
sure
ssu
rfac
ese
nsiti
vity
.T
his
prov
ides
stru
ctur
alin
form
atio
nth
atca
nbe
inte
rpre
ted
byw
ell-
know
nm
etho
ds.A
nex
trem
ely
high
X-r
ayfl
uxis
requ
ired
toob
tain
usef
ulda
tafr
omsi
ngle
-cry
stal
surf
aces
.Bul
kX
-ray
diff
ract
ion
isus
edto
dete
rmin
eth
est
ruct
ure
ofor
gano
met
allic
clus
ters
,whi
chpr
ovid
eco
mpa
riso
nsto
mol
ecul
esad
sorb
edon
surf
aces
.
Sur
face
stru
ctur
e
17
properties give rise to adhesion, friction, or sliding. Magnetic surfaces are used for infor-mation storage (e.g., magnetic tape or computer disk drive). Optical surface phenomenaare responsible for color and texture perception, total internal reflection needed for trans-mission through glass fibers, and the generation of second and higher harmonic frequenciesin nonlinear laser optics. The electrical behavior of surfaces often gives rise to surface chargebuildup, which is used for image transfer in xerography and for electron transport in inte-grated circuitry (Fig. 1.3).
Surfaces and interfaces are favorite media of evolution. Both photosynthetic and bio-logical systems, the brain (Fig. 1.4) and the leaf (Fig. 1.5), evolve and improve by everincreasing their interface area or their interface/volume ratio. The large number of foldsin the human brain (Fig. 1.4) helps to maximize the number of surface sites, whichalso facilitate charge transport and the transport of molecules. A leaf is a high-surface-area system designed to maximize the absorption of sunlight in order to carry outchlorophyll-catalyzed photosynthesis at optimum rates (Fig. 1.5). The spine of the seaurchin has remarkable strength that is achieved by the layered structure of an inorganic–organic composite, namely, single-crystalline calcium carbonate (CaCO3) that grows onordered layers of acidic macromolecules deposited on layers of protein (Fig. 1.6). Theseare but some of the examples that show how external surfaces are frequently usedin nature.
Figure 1.2. Interfaces are ever-present in our lives. (a) An astronaut representing the solid–vacuuminterface; (b) a jumping basketball player representing the solid–gas interface; (c) a sailboat represent-ing the solid–liquid interface; and (d) a tire representing the solid–solid interface. (See color insert.)
18 SURFACES: AN INTRODUCTION
Figure 1.3. Integrated microelectronic circuits are the heart of computers and other electronic devices.Miniaturization increases their speed and permits the performance of more functions per unit area. Aclose-up view of a transistor circuit element with the size of (a) 0.35 mm and (b) 70 nm. As theintegrated circuits are made increasingly more compact, their surface/volume ratio increases andessentially makes them surface devices. (c) The Intel Pentium 4 microprocessor. (Courtesy of PaulDavies, Intel Corporation.)
Figure 1.4. The intricate folds of the human brain expose the large interface area of this remarkableorgan. The brain may be viewed as a device with enormous solid–liquid interface area. (See colorinsert.)
1.2 SURFACES AND INTERFACES: CLASSIFICATION OF PROPERTIES 19
1.3 EXTERNAL SURFACES
1.3.1 Surface Concentration
The concentration of atoms or molecules at the surface of a solid or liquid can be estimatedfrom the bulk density. For a bulk density of 1 g cm23 (e.g., water), the molecular density r,in units of molecules per cubic centimeter (cm3), is �5 � 1022. The surface concentration of
Figure 1.5. The coleus leaf. Photosynthesis involves the absorption of sunlight and the reactions ofH2O and CO2 to produce organic molecules and oxygen. High-surface-area systems (e.g., the plantleaf) are most efficient to carry out photosynthesis. (Courtesy of Stefan Eberhard, ComplexCarbohydrate Research Center, The University of Georgia, Athens, GA.) (See color insert.)
Figure 1.6. Spine of a sea urchin. Schematic diagram of the composite layer structure that makes upthe spine of the sea urchin. Crystalline CaCO3 grows on an acidic macromolecular layer that is bound toprotein layers. The spine is a single crystal of CaCO3 with its 001 axis parallel to the growth axis.(Courtesy of S. Weiner, L. Addadi, and A. Berman, Weizmann Institute of Science, Rehovot, Israel.)
20 SURFACES: AN INTRODUCTION
molecules s (molecules cm22) is proportional to r2/3, assuming a cube-like packing, and isthus on the order of 1015 molecules cm22. Because the densities of most solids or liquids areall within a factor of 10 or so of each other, 1015 molecules cm22 is a good order-of-magnitudeestimate of the surface concentration of atoms or molecules for most solids or liquids. Ofcourse, surface atom concentration of crystalline solids may vary by a factor of 2 or 3, depend-ing on the type of packing of atoms at a particular crystal face.
1.3.1.1 Clusters and Small Particles. If a cluster is small enough, all of the atoms in thecluster are by necessity “surface atoms”. As a cluster grows in size, some atoms may becomecompletely surrounded by neighboring atoms and are thus no longer on the “surface”(Fig. 1.7). We frequently describe the concentration of surface atoms in a cluster with agiven size by its dispersion D, where D is the ratio of the number of surface atoms to thetotal number of atoms:
D ¼number of surface atoms
total number of atoms(1:1)
For very small particles, D is unity. As the particle grows and some atoms become sur-rounded by their neighbors, the dispersion decreases. The volume of a cluster is roughly pro-portional to d3, the cubic of the cluster size, as is the total number of atoms in the cluster.The surface area of a cluster is roughly proportional to d2. Therefore, the dispersion of a clus-ter is roughly to scale unit 1/d, the inverse of the cluster size (see right panel in Fig. 1.7).
Of course, the dispersion, D, also depends somewhat on the shape of the particle and howthe atoms are packed [177]. For two clusters with the same volume, but different shapes (e.g.,a cube and a sphere), the spherical cluster has a smaller surface area than the cubic cluster.Therefore, it is expected that, for the clusters to consist of the same number of atoms, the
0
0.2
0.4
0.6
0.8
1
0 20 40 60 80
d = 3.9 Å D = 1.0
d = 19.6 ÅD = 0.45
d = 11.8 Å D = 0.63
d = 15.7 Å D = 0.53
d = 7.8 ÅD = 0.78
Cluster size, d (Å)
Dis
per
sion
Figure 1.7. Cubic clusters with the face-centered cubic (fcc) packing of 14, 50, 110, 194, and 302atoms (the left panel). In the smallest cluster, all of the atoms are on the surface. However, the dis-persion defined as the number of surface atoms divided by the total number of atoms in the cluster,declines rapidly with increasing cluster size, which is shown in the right panel of the figure. Thesize d is the length of the edge of the cubic clusters. The lattice constant of the fcc clusters is assumedto be 3.9 A, which is close to that of the Pt crystal.
1.3 EXTERNAL SURFACES 21
rounder their shape, the lower the dispersion. Figure 1.8 compares the number of surfaceatoms on a cubic and a truncated cubic cluster. For a given total number of atoms, the trun-cated cubic cluster has fewer surface atoms than the cubic cluster.
Heterogeneous catalysts increase the rates of formation of product molecules and modifythe relative distribution of the products. Most catalysts, including those used to produce fuelsand chemicals ranging from high-octane gasoline to polyethylene (PE), are in the form ofsmall particles with a size range of 1–10 nm. This is because chemical reactions are facili-tated by surface atoms instead of bulk atoms. The increase in the dispersion of catalystslowers the material cost of producing the catalysts without changing their catalytic activity.
1.3.1.2 Thin Films. When metals or semiconductors are exposed to the atmosphere, athin layer of oxide is spontaneously formed on their surfaces. The oxide layer may not bevisible to your eyes since it is only a few nanometers thick, but it could serve as a protectivelayer against corrosion, or a insulation layer in the electronic devices, or an active phase incatalytic reactions.
Thin films are of great importance to many real-world problems. Their material costs arevery small compared to bulk materials, and they perform the same function when it comes tosurface processes. A monolayer of Rh (Fig. 1.9a), a very expensive metal, which containsonly �1015 metal atoms/cm22, can catalyze the reduction of nitrous oxide (NO) to dinitro-gen (N2) by its reaction with CO in the catalytic converter of an automobile. Diamond isthe hardest material in nature, but it is too expensive to be used directly for cutting anddrilling tools in the daily life. Deposition of diamond as a thin film on shaped tools again
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0 0.5 1 1.5 2Number of total atoms (×106)
Num
ber
of s
urfa
ce a
tom
s (×
106 )
Figure 1.8. Truncated cubic clusters with the fcc packing of 55 and 309 atoms (the upper panel). Thelower panel shows the number of surface atoms as a function of the total number of atoms for the cubiccluster (the solid line) and the truncated cubic cluster (the dashed line). Compared to the cubic cluster,the truncated cubic cluster is relatively rounder, so it has fewer atoms on the surface.
22 SURFACES: AN INTRODUCTION
can solve this problem (Fig. 1.9b). By using modern chemical vapor deposition or othervapor deposition techniques, a diamond layer as thick as a few micrometers (mm) can beroutinely grown on various substrates in order to improve the mechanical properties (e.g.,hardness and wear resistance) of cutting and drilling tools.
Modern computer information technology is all built on the devices with complexthin-film structures. The transistors shown in Figure 1.3a and b are made by alternativelydepositing and etching the thin films of Si and insulator materials. The hard drive disk forinformation storage is made of multiple thin layers on the top of a glass substrate(Fig. 1.9c). The first organic lubricant layer and the second hard C layer are used to protectthe surface against impact and scratching by the reading head. Under the operating con-ditions, the disk may spin as fast as 15,000 revolutions per minutes (rpm) and the readinghead is just �3 nm away from the surface, so the protective layers are the key to improvingthe lifetime of the hard drive. Under the protective layers, another multilayer forms themagnetic medium for information storage.
1.3.2 Internal Surfaces: Microporous Solids
Microporous solids are materials that are full of pores of molecular dimensions or larger.These materials have large internal surface areas. Many clays have layer structures that
Figure 1.9. (a) Schematic illustration of a surface covered with a monolayer of other material. (b) Ascanning electron microscopy (SEM) image of a diamond-coated microdrill. (c) A cross section of acomputer hard drive disk.
1.3 EXTERNAL SURFACES 23
can accommodate molecules between the layers by a process called intercalation. Graphitewill swell with water vapor to several times its original thickness (Fig. 1.10) as water mol-ecules become incorporated between the graphitic carbon layers.
Crystalline alumina silicates, often called zeolites, have ordered cages of moleculardimensions [178, 179] where molecules can adsorb or undergo chemical reactions(Fig. 1.11). These materials are also called molecular sieves, because they may preferentially
Figure 1.10. Intercalation compounds of graphite: C24K (top) and C8K (bottom). The color changesfrom black (graphite) are due to the transfer of electrons from the metal-to-carbon layers. (Courtesy ofTom Weller, Mark Ellerby and Neal Skipper, Department of Physics & Astronomy, London’s GlobalUniversity.) (See color insert.)
Figure 1.11. Microporous molecular sieve. There are many alumina silicates in nature that have poreswith molecular dimensions. These are called zeolites. Synthetic zeolites are also produced in largenumbers, mostly from silicates, phosphates, and borates. They are used as selective absorbers ofgases or liquids, and are the catalysts utilized in the largest volume in chemical and petroleum techno-logies. (See color insert.)
24 SURFACES: AN INTRODUCTION
adsorb certain molecules according to their size or polarizability. This property is of greatcommercial importance and may be used to separate mixtures of gases (air) or liquids orto carry out selective chemical reactions. Bones of mammals are made out of calcium apatite,which has a highly porous structure, with pores on the order of 10 nm (100 A) in diameter.Coal [180, 181] and char have porous structures, with pore diameters on the order of102–103 nm (103–104 A). These materials have a very large internal surface areas, in therange of 100–400 m2 g21 of solid. As this short survey has shown, nature has providedus with many useful microporous materials; and many synthetic microporous substancesare used in technology, both to separate gas and liquid mixtures by selective adsorptionand to carry out surface reactions selectively in their pores, which are often of moleculardimensions. Because surface reaction rate (product molecules formed per second) is pro-portional to surface area, materials with high internal surface areas carry out surface reactionsat very high rates.
1.4 CLEAN SURFACES
In order to study atomically clean surfaces, we must work under so-called ultrahigh vacuum(UHV) conditions [182–185], as the following rough calculation shows. We know that theconcentration of atoms on the surface of a solid is on the order of 1015 cm22. To keep thesurface clean for 1 s or 1 h, then, the flux of molecules incident on the initially clean surfacemust therefore be less than �1015 molecules21 cm22 s21 or �1012 molecules21 cm22 s21,respectively. From the kinetic theory of gases [186], the flux, F, of molecules striking thesurface of unit area at a given ambient pressure, P, is
F ¼NAPffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2pMRTp (1:2)
or
F (atoms�1 cm�2 s�1) ¼ 2:63� 1020 P (Pa)ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiM (g mol�1)T(K)
p (1:3)
or
F (atoms cm�2 s�1) ¼ 3:51� 1022 P (Torr)ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiM (g mol�1)T(K)
p (1:4)
where M is the average molar weight of the gaseous species, T is the temperature, and NA isAvogadro’s number. Substituting P ¼ 4 � 1024 Pa (3 � 1026 Torr) and using the valuesM ¼ 28 g mol21 and T ¼ 300 K, we obtain F ¼1015 molecules21 cm22 s21. Thus, atthis pressure the surface is covered with a monolayer of gas within seconds, assumingthat each incident gas molecule “sticks”. For this reason, the unit of gas exposure is1.33 � 1024 Pa-s (1026 Torr-s), which is called the Langmuir (L). Thus, a 1-L exposurewill cover a surface with a monolayer amount of gas molecules, assuming a sticking coeffi-cient of unity. At pressures on the order of 1.33 � 1027 Pa (1029 Torr), it may take 103 sbefore a surface is covered completely.
1.4 CLEAN SURFACES 25
In practice, one usually wants to study a surface without worrying about contaminationfrom ambient gases. Current surface-science techniques can easily detect contaminationon the order of 1% of a monolayer. Then, this will be our operational definition of“clean”. Thus, UHV conditions (,1.33 � 1027 Pa ¼ 1029 Torr) are required to maintaina clean surface for �1 h, the time usually needed to perform experiments on cleansurfaces.
1.5 INTERFACES
In most circumstances, however, and certainly in our Earth’s environment, surfaces arecontinually exposed to gases or liquids or placed in contact with other solids. As a result,we end up investigating the properties of interfaces (i.e., between a solid and gas, a solidand a liquid, a solid and a solid, and even between two immiscible liquids). Thus, unlessspecifically prepared otherwise, surfaces are always covered with a layer of atoms ormolecules from the neighboring phase (Fig. 1.12).
GAS
Liquid B
Liquid A
Liquid–gasinterface
Liquid–liquidinterface
Solid–liquidinterface
Soild
GAS
Solid–gasinterface
Solid–solidinterface
Solid B
Solid A
Figure 1.12. Schematic diagram of interfaces (e.g., solid–liquid, liquid–liquid, liquid–gas,solid–solid, and solid–gas interfaces).
26 SURFACES: AN INTRODUCTION
1.5.1 Adsorption
On approaching the surface, each atom or molecule encounters an attractive potential thatultimately will bind it to the surface under proper circumstances. The process that involvestrapping of atoms or molecules that are incident on the surface is called adsorption. It isalways an exothermic process. For historical reasons, the heat of adsorption, DHads isalways denoted as having a positive sign—unlike the enthalpy, DH, which for an exothermicprocess would be negative according to usual thermodynamic convention.
The residence time, r, of an adsorbed atom is given [187] by
t ¼ t0 expDHads
RT
� �(1:5)
where t0 is correlated with the surface atom vibration times (it is frequently on the order of10212 s), T is the temperature, and R is the gas constant. The value of t can be 1 s or longer at300 K for DHads . 63 kJ mol (15 kcal mol21). The surface concentration s (in moleculescm22) of adsorbed molecules on an initially clean surface is given by the product of the inci-dent flux, F, and the residence time
s ¼ Ft (1:6)
The surface of the material on which adsorption occurs is often called the substrate.Substrate–adsorbate bonds are usually stronger than the bonds between adsorbed molecules.As a result, the monolayer of adsorbate bonded to the substrate is held most tenaciously andis difficult to remove. Therefore, the properties of real surfaces are usually determined in thepresence of an adsorbed monolayer. For this reason, in the chapters that follow we will dis-cuss the various properties of surfaces when clean and also when covered with a monolayerof adsorbate.
1.5.2 Thickness of Surface Layers
A surface or interface may be defined as comprising of either one atomic layer or severallayers in the near-surface region. Usually, the phenomena or the systems studied definethe number of atomic layers that must be considered as part of the surface. For example,the chemical bond between an adsorbed molecule and atoms in the topmost atomic layerof a metal can be described rather well by considering the properties of one monolayer ofadsorbate and one monolayer of substrate atoms. However, the build up of charge at the sur-face of an electrical insulator may induce an electric field that extends .100 layers into thesolid. When such a surface is in contact with a liquid, the electric field due to the surfacecharge accumulation also extends into the liquid several molecular layers deep. In this cir-cumstance, the interface must be defined as many atomic layers thick on both sides of thesurface in order to properly describe the electrical properties of the interface.
1.6 THE TECHNIQUES OF SURFACE SCIENCE
Over the last four decades, a large number of techniques have been developed to study var-ious surface properties, including structure, composition, oxidation states, and changes of
1.6 THE TECHNIQUES OF SURFACE SCIENCE 27
chemical, electronic, and mechanical properties. The emphasis has been on surface probesthat monitor properties on the molecular level and are sensitive enough to detect ever smallernumbers of surface atoms. The frontiers of surface instrumentation are constantly beingpushed toward detection of finer detail: atomic spatial resolution, ever smaller energy resol-ution, and shorter time scales. Because no one technique provides all the necessary infor-mation about surface atoms, the tendency is to use a combination of techniques. The mostcommonly used techniques involve the scattering, absorption, or emission of photons, elec-trons, atoms, and ions, although some important surface-analysis techniques cannot beclassified this way.
Electrons, atoms, and ions are used primarily to investigate external surfaces and requirelow ambient pressures during their application. Photons can be used to study both internaland external surfaces because of their much lower scattering cross sections. They can alsobe employed at high-gas pressures and for studies of solid–liquid and solid–solid interfaces.
Because many surface probes require high vacuum during their application, most surfacescience instruments are also equipped with high-pressure or environmental cells. The sampleto be analyzed is first subjected to the usual high-pressure and/or high-temperature con-ditions encountered during reactions in the environmental cell. Then it is transferred intothe evacuated chamber where the surface probe is located for surface analysis. One suchapparatus is shown in Figure 1.13.
Sample preparation is always an important part of surface studies. Single crystals areoriented by X-ray back-diffraction, cut, and polished. They are then ion bombarded orchemically treated to remove undesirable impurities from their surfaces.
Thin films are deposited from vapor by sublimation, sputtering, or the use of plasma-assisted chemical vapor deposition. Materials of high internal surface area are preparedfrom a sol–gel or by calcination at high temperatures. The genesis and environmental historyof the surface is primarily responsible for its structure and composition and must always becarefully monitored.
Figure 1.13. Photograph of a stainless steel chamber used for surface studies. It is equipped with sur-face characterization instruments that are used in UHV and with a high-pressure cell that is shown inboth open (a) and closed (b) positions. The cell is used to expose the samples to high pressures andtemperatures. The chamber can be evacuated to 10210 Torr and equipped with windows on steel flangeswith glass–metal seals for easy viewing. The flanges are mounted using Cu gaskets to avoid the use oflubricated seals so that the chamber can be “baked” at high temperatures (�2008C) to clean its internalsurfaces. A manipulator that is used to mount the sample provides motion in three dimensions (3D) andpermits cooling and heating. Gas analysis is provided by a mass spectrometer mounted on the chamber.The pressure is measured by ionization and thermocouple gauges.
28 SURFACES: AN INTRODUCTION
Table 1.1 lists many of the surface science techniques that have been used most frequentlyin recent years to learn about the interface on the atomic scale [15–187]. The names of thetechniques, their acronyms, and brief descriptions are provided, along with references, if amore detailed study of the capabilities and limitations of a particular technique is desired.We also indicate the primary surface information that can be obtained by the applicationof each technique. Detailed discussions of these techniques are outside the scope of thisbook. The reader is referred to review papers that describe the principles of operation foreach, the instrumentation, and some of the findings of the experiments that used this tech-nique. Many surface-science techniques are used in combination to obtain a more completecharacterization of the structure (atomic, molecular, electronic) and the composition (includ-ing oxidation states) of atoms and molecules at the interface with increasing spatial and timeresolution.
1.7 SUMMARY AND CONCEPTS
† The surface concentration of atoms or molecules is on the order of 1015 for most solidsand liquids.
† Small particles used in surface studies are frequently described in terms of theirdispersion.
† Thin films and microporous solids are systems with high surface/volume ratios.† Many surface-science studies focus on interfaces (solid–gas, solid–liquid, and solid–
solid), since surfaces are covered with adsorbates under the practical conditions inwhich they are utilized.
† The definition of how many atomic layers constitute the “surface region” depends onthe surface phenomena under investigation. For example, one atomic or molecularlayer can be responsible for most surface chemical properties, whereas almost 103
layers are required to investigate surface effects in electron or photon transport.† Most techniques provide information on only one side of the surface–adsorbate bond.
Future instrumentation developments aim for molecular level studies at buried inter-faces, of both sides of the surface chemical bonds, and on an ever shorter time scale(time-resolved studies).
† Photon, electron, atom, and ion scattering are utilized most frequently to study surfaceatomic and electronic structures and composition. Vacuum or reduced pressures at theinterface is needed during experiments using electrons, atoms, and ions. As a result, weknow more about the properties of the solid–vacuum and solid–gas interfaces thanabout solid–liquid, solid–solid, and liquid–liquid interfaces.
† Clean, adsorbate-free surfaces must be prepared in UHV.† Selective adsorption of atoms and molecules are also important tools for studies of
surface composition and bonding.
1.8 PROBLEMS
1.1 Calculate the concentration of surface atoms (atoms cm22) for a droplet ofmercury (Hg), a piece of copper (Cu) and a drop benzene (C6H6).
1.2 (a) What is the gas flux striking a surface in air at 1 atm and 300 K?
1.8 PROBLEMS 29
(b) Calculate the pressure necessary to keep a 1-cm2 Cu surface clean for 1 h at 300 K,assuming a sticking coefficient of 1 and no dissociation of the gas upon adsorption.
1.3 In most cases, of course, the sticking coefficients are� 1. Using the following stickingcoefficient for O2, calculate the pressure necessary to keep a 1-cm2 Cu surface “clean”for 1 s, 1 h, and 8 h at 300 K (the latter times correspond to times for “fast” or “relaxed”experiments, respectively). According to Ref. [188], s ¼ 0.01, 0.2, and 0.001 for the(100), (110), and (111) faces of Cu, respectively.
1.4 At 1-atm air pressure, compute the volume of N2 gas that is adsorbed on 10 g of zeolitewith a surface area of 400 m2 g21. Assume a surface area of 16.2 A2 per nitrogenmolecule.
1.5 What is the residence time of molecular nitrogen in a zeolite at 77 and 300 K? Assumea heat of adsorption of 15 kJ mol21 and t0 ¼ 10212 s.
REFERENCES
1. J. Berzelius. Jahres-Bericht uber die Fortschritte der Physichen Wissenschaften. Tubingen,1836.
2. J.M. Thomas. Michael Faraday and the Royal Institution. IOP Publishing, Bristol, 1991.
3. W. Ostwald. Electrochemistry: History and Theory. Amerind Publishing Co. Pvt. Ltd., NewDelhi, 1980.
4. J.B. Hudson. Surface Science: An Introduction. Butterworth–Heinemann, Boston, 1992.
5. D.P. Woodruff and T.A. Delchar. Modern Techniques of Surface Science. Cambridge Solid StateScience Series. Cambridge University Press, New York, 1986.
6. M.J. Higatsberger. Solid Surfaces Analysis. In C. Marton, editor(s), Advances in Electronics andElectron Physics, Volume 56. Academic Press, New York, 1981.
7. E. Hulpke. Helium Atom Scattering from Surfaces. Springer Series in Surface Sciences. Ineditor(s), Volume 27. Springer-Verlag, Berlin, 1992.
8. B. Poelsema and G. Comsa. Scattering of Thermal Energy Atoms from Disordered Surfaces. InG. Holder, editor(s), Springer Tracts in Modern Physics, Volume 115. Springer-Verlag, Berlin,1989.
9. J.A. Barker and D.J. Auerbach. Surf. Sci. Rep. 4:1 (1984).
10. D.P. Woodruff, G.C. Wang, and T.M. Lu. Surface Structure and Order–Disorder Phenomena.In D.A. King and D.P. Woodruff, editor(s), Adsorption at Solid Surfaces, The Chemical Physicsof Solid Surfaces and Heterogeneous Catalysis, Volume 2. Elsevier, New York, 1983.
11. D. Frankl. Prog. Surf. Sci. 13:285 (1983).
12. D.P. Woodruff. Surface Periodicity, Crystallography and Structure. In D.A. King andD.P. Woodruff, editor(s), Clean Solid Surfaces. The Chemical Physics of Solid Surfaces andHeterogeneous Catalysis, Volume 1. Elsevier, New York, 1981.
13. G.A. Somorjai and M.A.V. Hove. Adsorbed Monolayers on Solid Surfaces. In J.D. Dunitz et al.,editor(s), Structure and Bonding, Volume 38. Springer-Verlag, Berlin, 1979.
14. H. Wagner. Physical and Chemical Properties of Stepped Surfaces. In G. Hohler, editor(s),Solid Surface Physics. Springer Tracts in Modern Physics, Volume 85. Springer-Verlag,Berlin, 1979.
15. F.O. Goodman. Scattering of Atoms and Molecules by Solid Surfaces. In R. Vanselow, editor(s),Critical Reviews in Solid State and Material Sciences, Volume 7. CRC Press, Boca Raton, FL,1977.
30 SURFACES: AN INTRODUCTION
16. R. Browning. Auger Spectroscopy and Scanning Auger Microscopy. In D.J. O’Conner,B. A. Sexton, and R.S.C. Smart, editor(s), Surface Analysis Methods in Materials Science,Springer Series in Surface Sciences, Volume 23. Springer-Verlag, Berlin, 1992.
17. J.M. Slaughter et al. MRS Bull. December: 39 (1992).
18. R.L. Park. Core-Level Spectroscopies. In R.L. Park and M.G. Lagally, editor(s), Solid StatePhysics: Surfaces, Methods of Experimental Physics, Volume 22. Academic Press, New York,1985.
19. R.L. Park. Appl. Surf. Sci. 4:250 (1980).
20. L.E. Davis et al. Handbook of Auger Electron Spectroscopy, Perkin Elmer, Eden Prairie, MN,1978.
21. B.V. King. Sputter Depth Profiling. In D.J. O’Conner, B.A. Sexton, and R.S.C. Smart, editor(s),Surface Analysis Methods in Materials Science. Springer Series in Surface Sciences, Volume 23.Springer-Verlag, Berlin, 1992.
22. R.P.H. Gasser. An Introduction to Chemisorption and Catalysis by Metals. Oxford UniversityPress, New York, 1985.
23. R. Weissmann and K. Muller. Surf. Sci. Rep. 1:251 (1981).
24. M. Prutton. Surface Physics. Oxford University Press, New York, 1975.
25. G. Ertl and J. Kupper. Low Energy Electrons and Surface Chemistry. VCH, Weinheim,Germany, 1985.
26. J. Kirschner. Polarized Electrons at Surfaces. In G. Hohler, editor(s), Springer Tracts in ModernPhysics, Volume 106. Springer-Verlag, Berlin, 1985.
27. G.E. McGuire and P.H. Holloway. Applications of Auger Spectroscopy in Materials Analysis. InC.R. Brundle and A.D. Baker, editor(s), Electron Spectroscopy: Theory, Techniques andApplications, Volume 4. Academic Press, New York, 1981.
28. J.C. Fuggle. High Resolution Auger Spectroscopy of Solids and Surfaces. In C.R. Brundle andA.D. Baker, editor(s), Electron Spectroscopy: Theory, Techniques and Applications, Volume4. Academic Press, New York, 1981.
29. C.C. Chang. Analytical Auger Electron Spectroscopy. In P.F. Kane and G.B. Larrabee, editor(s),Characterization of Solid Surfaces, Plenum Press, New York, 1974.
30. P.M. Hall and J.M. Morabito. Compositional Depth Profiling by Auger Electron Spectroscopy. InR. Vanselow, editor(s), Chemistry and Physics of Solid Surfaces, Volume 2. CRC Press, BocaRaton, FL, 1979.
31. A. Joshi, L.E. Davis, and P.W. Palmberg. Auger Electron Spectroscopy. In A.W. Czanderna,editor(s), Methods of Surface Analysis. Methods and Phenomena: Their Applications inScience and Technology, Volume 1. Elsevier, New York, 1975.
32. E. Meyer. Prog. Surf. Sci. 41:1 (1992).
33. D. Rugar and P. Hansma. Phys. Today October: 23 (1990).
34. S.A.C. Gould et al. J. Vacuum Sci. Technol. A 8:369 (1990).
35. E. Meyer et al. Thin Solid Films 181:527 (1989).
36. N.A. Burnham and R.J. Colton. J. Vacuum Sci. Technol. A 7:2906 (1989).
37. P.K. Hansma et al. Science. 242:157 (1988).
38. P.K. Hansma and J. Tersoff, J. Appl. Phys. 61(2):R1 (1987).
39. G. Binnig, C.F. Quate, and C. Gerber. Phys. Rev. Lett. 56:930 (1986).
40. C.S. Fadley. The Study of Surface Structures by Photoelectron Diffraction and Auger ElectronDiffraction. In R.Z. Bachrach, editor(s), Synchrotron Radiation Research. Advances in Surfaceand Interface Science, Volume I: Techniques, Plenum Press, New York, 1992.
REFERENCES 31
41. D.P. Woodruff. Photoelectron Diffraction. In S.D. Kevan, editor(s), Angle-ResolvedPhotoemission: Theory and Current Applications, Studies in Surface Science and Catalysis,Volume 74. Elsevier, New York, 1992.
42. J.J. Barton, S.W. Robey, and D.A. Shirley. Phys. Rev. B 34:778 (1986).
43. N.V. Richardson and A.M. Bradshaw. Symmetry and the Electron Spectroscopy of Surfaces. InC.R. Brundle and A.D. Baker, editor(s), Electron Spectroscopy: Theory, Techniques andApplications, Volume 4. Academic Press, New York, 1981.
44. G. Margaritondo and J.H. Weaver. Photoemission Spectroscopy of Valence States. In R.L. Parkand M.G. Lagally, editor(s), Solid State Physics: Surfaces, Methods of Experimental Physics,Volume 22. Academic Press, New York, 1985.
45. W. Eberhardt. Angle-Resolved Photoemission Spectroscopy. In R.Z. Bachrach, editor(s),Synchrotron Radiation Research. Advances in Surface and Interface Science, Volume I:Techniques, Plenum Press, New York, 1992.
46. K.E. Smith and S.D. Kevan. Prog. Solid State Chem. 21:49 (1991).
47. N.V. Smith and S.D. Kevan. Introduction. In S.D. Kevan, editor(s), Angle-ResolvedPhotoemission: Theory and Current Applications, Studies in Surface Science and Catalysis,Volume 74. Elsevier, New York, 1992.
48. F.J. Himpsel. Adv. Phys. 32:1 (1983).
49. M. Scheffler and A.M. Bradshaw. The Electronic Structure of Adsorbed Layers. In D.A. Kingand D.P. Woodruff, editor(s), Adsorption at Solid Surfaces, The Chemical Physics of SolidSurfaces and Heterogeneous Catalysis, Volume 2. Elsevier, New York, 1983.
50. J.E. Inglesfield and B.W. Holland. Electrons at Surfaces. In D.A. King and D.P. Woodruff, edi-tor(s), Clean Solid Surfaces, The Chemical Physics of Solid Surfaces and HeterogeneousCatalysis, Volume 1. Elsevier, New York, 1981.
51. A.P. Kaduwela, D.J. Friedman, and C.S. Fadley. J. Electron Spectros. Relat. Phenom. 57:223(1991).
52. C.S. Fadley. Prog. Surf. Sci. 16:275 (1984).
53. S.Y. Tong and C.H. Li. Diffraction Effects in Angle-Resolved Photoemission Spectroscopy. InR. Vanselow and W. England, editor(s), Chemistry and Physics of Solid Surfaces, Volume 3.CRC Press, Boca Raton, FL, 1982.
54. F.J. Berry. Mossbauer Spectroscopy. In B.W. Rossiter and R.C. Baetzold, editor(s),Determination of Structural Features of Crystalline and Amorphous Solids. Physical Methodsof Chemistry, Volume 5, 2nd edition. John Wiley & Sons, Inc., New York, 1990.
55. T.E. Cranshaw et al. Mossbauer Spectroscopy and Its Applications. Cambridge University Press,New York, 1985.
56. W. Jones et al. Appl. Surf. Sci. 1:388 (1978).
57. M.J. Tricker, J.M. Thomas, and A.P. Winterbottom. Surf. Sci. 45:601 (1974).
58. R.L. Park. Appl. Surf. Sci. 13:231 (1982).
59. N. Sheppard. Ann. Rev. Phys. Chem. 39:589 (1988).
60. H. Ibach and D.L. Mills. Electron Energy Loss Spectroscopy and Surface Vibrations. AcademicPress, New York, 1982.
61. R.F. Willis, A.A. Lucas, and G.D. Mahan. Vibrational Properties of Adsorbed Molecules. InD.A. King and D.P. Woodruff, editor(s), Adsorption at Solid State Surfaces. The ChemicalPhysics of Solid Surfaces and Heterogeneous Catalysis, Volume 2. Elsevier, New York, 1983.
62. W.H. Weinberg. Vibrations in Overlayers. In R.L. Park and M.G. Lagally, editor(s), Solid StatePhysics: Surfaces. Methods of Experimental Physics, Volume 22. Academic Press, New York,1985.
32 SURFACES: AN INTRODUCTION
63. D.T. Clark. Structure, Bonding, and Reactivity of Polymer Surfaces Studies by Means of ESCA.In R. Vanselow, editor(s), Chemistry and Physics of Solid Surfaces, Volume 2. CRC Press, BocaRaton, FL, 1979.
64. D. Briggs. Analytical Applications of XPS. In C.R. Brundle and A.D. Baker, editor(s), ElectronSpectroscopy: Theory, Techniques and Applications, Volume 3. Academic Press, New York,1979.
65. W.M. Riggs and M.J. Parker. Surface Analysis by X-Ray Photoelectron Spectroscopy. InA.W. Czanderna, editor(s), Methods of Surface Analysis. Methods and Phenomena: TheirApplications in Science and Technology, Volume 1. Elsevier, New York, 1975.
66. R.D. Ramsier and J.T. Yates, Jr. Surf. Sci. Rep. 12:243 (1991).
67. V. Rehn and R.A. Rosenberg. Photon-Stimulated Desorption. In R.Z. Bachrach, editor(s),Synchrotron Radiation Research. Advances in Surface and Interface Science, Volume I:Techniques, Plenum Press, New York, 1992.
68. R.H. Stulen. Prog. Surf. Sci. 32:1 (1989).
69. M.L. Knotek. Rep. Prog. Phys. 47:1499 (1984).
70. M.L. Knotek. Phys. Today September: 24 (1984).
71. T.E. Madey and R. Stockbauer. Experimental Methods in Electron- and Photon-StimulatedDesorption. In R.L. Park and M.G. Lagally, editor(s), Solid State Physics: Surfaces. Methodsof Experimental Physics, Volume 22. Academic Press, New York, 1985.
72. F.K. Urban III. Appl. Surf. Sci. 33/34:934 (1988).
73. S.M. Heald and J.M. Tranquada. X-Ray Absorbtion Spectroscopy: EXAFS and XANES. InB.W. Rossiter and R.C. Baetzold, editor(s), Determination of Structural Features ofCrystalline and Amorphous Solids. Physical Methods of Chemistry, Volume 5, 2nd edition.John Wiley & Sons, Inc., New York, 1990.
74. D.P. Woodruff. Rep. Prog. Phys. 49:683 (1986).
75. P. Lagarde and H. Dexpert. Adv. Phys. 33:567 (1984).
76. S.M. Heald. Design of an EXAFS Experiment. In D.C. Koningsberger and R. Prins, editor(s),X-Ray Absorption. Chemical Analysis, Volume 92. John Wiley & Sons, Inc., New York, 1988.
77. B.K. Teo. EXAFS: Basic Principles and Data Analysis. Springer-Verlag, Berlin, 1986.
78. E.A. Stern. Theory of EXAFS. In D.C. Koningsberger and R. Prins, editor(s), X-Ray Absorption.Chemical Analysis, Volume 92. John Wiley & Sons, Inc., New York, 1988.
79. J. Derrien et al. Surf. Sci. 189/190:590 (1987).
80. R. Gomer. Recent Applications of Field Emission Microscopy. In R. Vanselow, editor(s),Chemistry and Physics of Solid Surfaces, Volume 2. CRC Press, Boca Raton, FL, 1979.
81. J.A. Panitz. High-Field Techniques. In R.L. Park and M.G. Lagally, editor(s), Solid StatePhysics: Surfaces. Methods of Experimental Physics, Volume 22. Academic Press, New York,1985.
82. G. Ehrlich. Phys. Today June: 44 (1981).
83. N.K. Roberts. Fourier Transform Infrared Spectroscopy of Surfaces. In D.J. O’Conner,B.A. Sexton, and R.S.C. Smart, editor(s), Surface Analysis Methods in Materials Science.Springer Series in Surface Sciences, Volume 23. Springer-Verlag, Berlin, 1992.
84. D.M. Back. Fourier Transform Infrared Analysis of Thin Films. In M.H. Francombe andJ.L. Vossen, editor(s), Thin Films for Advanced Electronic Devices. Physics of Thin Films,Volume 15. Academic Press, New York, 1991.
85. Y.J. Chabal. Surf. Sci. Rep. 8:211 (1988).
86. I. Stensgaard. Rep. Prog. Phys. 55:989 (1992).
REFERENCES 33
87. L.C. Feldman. MeV Ion Scattering for Surface Structure Determination. In R. Vanselow andW. England, editor(s), Critical Reviews in Solid State and Material Sciences, Volume 10.CRC Press, Boca Raton, FL, 1981. p. 411.
88. H. Bluhm et al. MRS Bull. 32:1022 (2007).
89. M. Salmeron and R. Schlogl. Surf. Sci. Rep. 63:169 (2008).
90. W. Ho. High Resolution Electron Energy Loss Spectroscopy. In B.W. Rossiter andR.C. Baetzold, editor(s), Investigations of Surfaces and Interfaces, Part A. of PhysicalMethods of Chemistry, Volume 9A, 2nd edition. John Wiley & Sons, Inc., New York, 1993.p. 411.
91. J.L. Erskine. High Resolution Electron Energy Loss Spectroscopy. In J.E. Greene, editor(s),Critical Reviews in Solid State and Material Sciences, Volume 13. CRC Press, Boca Raton,FL, 1987.
92. J.J. Pireaux et al. Surf. Interface Anal. 15:189 (1990).
93. H.D. Hagstrum. Studies of Adsorbate Electronic Structure Using Ion Neutralization andPhotoemission Spectroscopies. In L. Fiermanns, J. Vennik, and V. Dekeyser, editor(s), NATOAdvanced Study Institutes Series: Series B, Physics, Volume 32. Plenum Press, 1978.
94. P.D. Johnson. Inverse Photoemission. In S.D. Kevan, editor(s), Angle-Resolved Photoemission:Theory and Current Applications. Studies in Surface Science and Catalysis, Volume 74.Elsevier, New York, 1992.
95. F.J. Himpsel. Surf. Sci. Rep. 12:1 (1990).
96. G. Borstel and G. Thorner. Surf. Sci. Rep. 8:1 (1987).
97. N.V. Smith and D.P. Woodruff. Prog. Surf. Sci. 21:295 (1986).
98. V. Dose. Surf. Sci. Rep. 5:337 (1985).
99. V. Dose. Prog. Surf. Sci. 13:225 (1983).
100. F.M. Hoffmann. Surf. Sci. Rep. 3:107 (1983).
101. H.G. Tompkins. Infrared Reflection-Absorption Spectroscopy. In A.W. Czandrna, editor(s),Methods of Surface Analysis. Methods and Phenomena: Their Applications in Science andTechnology, Volume 1. Elsevier, New York, 1975.
102. E. Taglauer. Ion Scattering Spectroscopy. In A.W. Czandema and D.M. Hercules, editor(s), IonSpectroscopies for Surface Analysis. Methods of Surface Characterization, Volume 2. PlenumPress, New York, 1991.
103. W. Heiland and E. Taglauer. Ion Scattering and Secondary-Ion Mass Spectrometry. In R.L. Parkand M.G. Lagally, editor(s), Solid State Physics: Surfaces. Methods of Experimental Physics,Volume 22. Academic Press, New York, 1985.
104. P.R. Watson. J. Phys. Chem. Ref. Data 19:85 (1990).
105. M.A.V. Hove. Proc. R. Soc. London Ser. A 442:61 (1993).
106. G.A. Somorjai and M.A.V. Hove. Surface Crystallography by Low-Energy Electron Diffraction.In B.W. Rossiter, J.F. Hamilton, and R.C. Baetzold, editor(s), Investigation of Interfaces andSurfaces, Interscience Publishers, Rochester, NY, 1990.
107. M.A.V. Hove, W.H. Weinberg, and C.M. Chan. Low Energy Electron Diffraction. In G. Ertl,editor(s), Springer Series in Surface Sciences, Volume 6. Springer-Verlag, Berlin, 1986.
108. J.B. Pendry. Low Energy Electron Diffraction. Academic Press, New York, 1974.
109. P.R. Watson. J. Phys. Chem. Ref. Data 16:953 (1987).
110. D.J. O’Conner. Low Energy Ion Scattering. In D.J. O’Conner, B.A. Sexton, and R.S.C. Smart,editor(s), Surface Analysis Methods in Materials Science. Springer Series in Surface Sciences,Volume 23. Springer-Verlag, Berlin, 1992.
34 SURFACES: AN INTRODUCTION
111. T.M. Buck. Low-Energy Ion Scattering Spectrometry. In A.W. Czandema, editor(s), Methods ofSurface Analysis. Methods and Phenomena: Their Applications in Science and Technology,Volume 1. Elsevier, New York, 1975.
112. K.F. Canter. Current Status of Low Energy Position Diffraction. In P.J. Schultz, G.R. Massoumi,and P.J. Simpson, editor(s), Positron Beams for Solids and Surfaces. AIP ConferenceProceedings, Volume 218. American Institute of Physics, New York, 1990.
113. K.F. Canter, C.B. Duke, and A.P. Mills, Jr. Current Status of Low Energy Position Diffraction. Ineditor(s), Proceedings of the Ninth International Summer Institute in Surface Science, Springer-Verlag, Berlin, 1989.
114. R.E. Lechner and C. Riekel. Applications of Neutron Scattering in Chemistry. In G. Hohler,editor(s), Neutron Scattering and Muon Spin Rotation. Springer Tracts in Modern Physics,Volume 101. Springer-Verlag, Berlin, 1983.
115. J.P. McTague, M. Nielson, and L. Passell. Neutron Scattering by Adsorbed Monolayers. InR. Vanselow, editor(s), Chemistry and Physics of Solid Surfaces, Volume 2. CRC Press, BocaRaton, FL, 1979.
116. C.J. Wright and C.M. Sayer. Rep. Prog. Phys. 46:773 (1983).
117. J. Stohr. NEXAFS Spectroscopy. Springer Series in Surface Sciences. Volume 25. Springer-Verlag, Berlin, 1992.
118. A. Bianconi and A. Marcelli. X-Ray Absorbtion Near-Edge Structure: Surface XANES. InR.Z. Bachrach, editor(s), Synchrotron Radiation Research. Advances in Surface and InterfaceScience, Volume I: Techniques, Plenum Press, New York, 1992.
119. A. Bianconi. XANES Spectrocopy. In D.C. Koningsberger and R. Prins, editor(s), X-RayAbsorption. Chemical Analysis, Volume 92. John Wiley & Sons, Inc., 1988.
120. T.M. Duncan and C. Dybowski. Surf. Sci. Rep. 1:157 (1981).
121. P.J. Barrie and J. Klinowski. Prog. Nucl. Magn. Reson. 24:91 (1992).
122. W.G. Golden et al. J. Phys. Chem. 88:574 (1984).
123. P. Galletto et al. Design of a Polarization-Modulation Infrared Spectroscopy (PM-IRAS)Experiment for In-situ Studies of Model Catalysts. In Malmo, Sweden, 2 pp. (2002).
124. G. Rupprechter. Advances in Catalysis 51:133 (2007).
125. L.C. Feldman. Rutherford Backscattering and Nuclear Reaction Analysis. In A.W. Czandernaand D.M. Hercules, editor(s), Ion Spectroscopies for Surface Analysis. Methods of SurfaceCharacterization, Volume 2. Plenum Press, New York, 1991.
126. J.F.v.d. Veen. Surf. Sci. Rep. 5:199 (1985).
127. G.L. Price. Reflection High Energy Electron Diffraction. In D.J. O’Conner, B.A. Sexton, andR.S.C. Smart, editor(s), Surface Analysis Methods in Materials Science. Springer Series inSurface Sciences, Volume 23. Springer-Verlag, Berlin, 1992.
128. D.P. Woodruff. Surf. Interface Anal. 11:25 (1988).
129. M.D. Crescenzi. Extended Energy Loss Fine Structure Analysis. In J.E. Greene, editor(s),Critical Reviews in Solid State and Material Sciences, Volume 15. CRC Press, Boca Raton,FL, 1989.
130. P.R. Watson. J. Phys. Chem. Ref. Data 21:123 (1992).
131. I. Pockrand. Surface Enhanced Raman Vibrational Studies at Solid/Gas Interfaces. In G. Hohler,editor(s), Springer Tracts in Modern Physics, Volume 104. Springer-Verlag, 1984.
132. M. Moskovits. Rev. Mod. Phys. 57:783 (1985).
133. J.E. Rowe. Surface EXAFS. In R.Z. Bachrach, editor(s), Synchrotron Radiation Research.Advances in Surface and Interface Science, Volume I: Techniques, Plenum Press, New York,1992.
REFERENCES 35
134. J. Stohr. SEXAFS: Everything You Always Wanted to Know about SEXAFS but Were Afraid toAsk. In D.C.K.a.R. Prins, editor(s), X-Ray Absorption. Chemical Analysis, Volume 92. JohnWiley & Sons, Inc., New York, 1988.
135. P. Eisenberger et al. SEXAFS: New Horizons in Surface Structure Determinations. InR. Vanselow and W. England, editor(s), Chemistry and Physics of Solid Surfaces, Volume 3.CRC Press, Boca Raton, FL, 1982.
136. J.N. Israelachvili. Surf. Sci. Rep. 14:109 (1992).
137. J.N. Israelachvili and P.M. McGuiggan. J. Mater. Res. 5:2223 (1990).
138. J.L. Parker, H.K. Christenson, and B.W. Ninham. Rev. Sci. Instrum. 60:3135 (1989).
139. J.N. Israelachvili. Intermolecular and Surface Forces. Academic Press, London, 1985.
140. Y.R. Shen. Nature (London). 337:519 (1989).
141. P. Guyot-Sionnest, R. Superfine, J.H. Hunt, and Y.R. Shen, Sum-Frequency Generationfor Surface Vibrational Spectroscopy. In Z. Wang and Z. Zhang, editor(s), Proceedings ofthe Topical Meeting on Laser Materials and Laser Spectroscopy, World Scientific Press,Singapore, 1989.
142. Y.R. Shen. Annu. Rev. Phys. Chem. 40:327 (1989).
143. W. Chen, et al. Second Harmonic Generation Studies of Liquid Crystal Monolayers and Films. InT.F. George, editor(s), Photochemistry in Thin Films. Proceedings of the Society of Photo-Optical Instrumentation Engineers, Volume 1056. Society of Photo-Optical InstrumentationEngineers, Bellingham, WA, 1989.
144. G.L. Richmond, J.M. Robinson, and V.L. Shannon. Prog. Surf. Sci. 28:1 (1988).
145. C.M. Greenlief and J.M. White. Secondary Ion Mass Spectroscopy. In B.W. Rossiter andR.C. Baetzold, editor(s), Investigations of Surfaces and Interfaces, Part A. Physical Methodsof Chemistry, Volume 9A, 2nd edition. John Wiley & Sons, Inc., New York, 1993.
146. R.J. MacDonald and B.V. King. SIMS—Secondary Ion Mass Spectroscopy. In D.J. O’Conner,B.A. Sexton, and R.S.C. Smart, editor(s), Surface Analysis Methods in Materials Science.Springer Series in Surface Sciences, Volume 23. Springer-Verlag, Berlin, 1992.
147. J.C. Vickerman, A. Brown, and N.M. Reed, editor(s), Secondary Ion Mass Spectrometry.International Series of Monographs in Chemistry, Volume 17, Clarendon Press, Oxford, 1989.
148. R.G. Wilson, F.A. Stevie, and C.W. Magee. Second Ion Mass Spectrometry: A PracticalHandbook for Depth Profiling and Bulk Impurity Analysis. John Wiley & Sons, New York, 1989.
149. A. Benninghoven, F.G. Rudenauer, and H.W. Werner. Secondary Ion Mass Spectrometry: BasicConcepts, Instrumental Aspects, Applications and Trends. Chemical Analysis. John Wiley &Sons, Inc., New York, 1987.
150. H.W. Werner. Introduction to Secondary Ion Mass Spectrometry (SIMS). In L. Fiermanns,J. Vennik, and V. Dekeyser, editor(s), NATO Advanced Study Institutes Series: Series B,Physics, Volume 32. Plenum Press, 1978.
151. J.A. McHugh. Secondary Ion Mass Spectrometry. In A.W. Czanderna, editor(s), Methods ofSurface Analysis. Methods and Phenomena: Their Applications in Science and Technology,Volume 1. Elsevier, New York, 1975.
152. R. Feder et al. Surf. Sci. 444:419 (1981).
153. A.L.d. Lozanne. Scanning Tunneling Microscopy. In B.W. Rossiter and R.C. Baetzold, editor(s),Investigations of Surfaces and Interfaces, Part A. Physical Methods of Chemistry, Volume 9A,2nd edition. John Wiley & Sons, Inc., New York, 1993.
154. B.A. Sexton. Scanning Tunneling Microscopy. In D.J. O’Conner, B.A. Sexton, andR.S.C. Smart, editor(s), Surface Analysis Methods in Materials Science. Springer Series inSurface Sciences, Volume 23. Springer-Verlag, Berlin, 1992.
36 SURFACES: AN INTRODUCTION
155. H.J. Gunterodt and R. Wiesendanger. Scanning Tunneling Microscopy I: General Principles andApplications to Clean and Adsorbate Covered Surfaces. Springer Series in Surface Sciences. Ineditor(s), Volume 20. Springer-Verlag, Berlin, 1992.
156. L.E.C.v.d. Leemput and H.V. Kempen. Rep. Prog. Phys. 55:165 (1992).
157. M. Tsukada et al. Surf. Sci. Rep. 13:265 (1991).
158. F. Ogletree and M. Salmeron. Prog. Solid State Chem. 20:235 (1990).
159. G. Binnig and H. Rohrer. Rev. Mod. Phys. 59:615 (1987).
160. J.M. Cowley. Prog. Surf. Sci. 21:209 (1986).
161. G. Thomas. Ultramicroscopy 20:239 (1986).
162. A.M.d. Jong and J.W. Niemantverdriet. Surf. Sci. 233:355 (1990).
163. D.A. King. Surf. Sci. 47:384 (1975).
164. J.T. Yates. The Thermal Desorption of Adsorbed Species. In R.L. Park and M.G. Lagally, edi-tor(s), Solid State Physics: Surfaces. Methods of Experimental Physics, Volume 22. AcademicPress, New York, 1985.
165. R.J. Madix. The Application of Flash Desorption Spectroscopy to Chemical Reactions onSurfaces; Temperature Programmed Reaction Spectroscopy. In R. Vanselow, editor(s),Chemistry and Physics of Solid Surfaces, Volume 2. CRC Press, Boca Raton, FL, 1979.
166. J.L. Beeby. The Theory of Desorption. In R. Vanselow, editor(s), Critical Reviews in Solid Stateand Material Sciences, Volume 7. CRC Press, Boca Raton, FL, 1977.
167. R. Leckey. Ultraviolet Photoelectron Spectroscopy of Solids. In D.J. O’Conner, B.A. Sexton, andR.S.C. Smart, editor(s), Surface Analysis Methods in Materials Science. Springer Series ofSurface Sciences, Volume 23. Springer-Verlag, Berlin, 1992.
168. W.E. Spicer. The Use of Synchrotron Radiation in UPS: Theory and Results. In L. Fiermanns,J. Vennik, and V. Dekeyser, editor(s), NATO Advanced Study Institutes Series: Series B,Physics, Volume 32. Plenum Press, New York, 1978.
169. J. Holzl and F.K. Schulte. Work Function of Metals. In G. Hohler, editor(s), Solid SurfacePhysics. Springer Tracts in Modern Physics, Volume 85. Springer-Verlag, Berlin, 1979.
170. L.W. Swanson and P.R. Davis. Work Function Measurements. In R.L. Park and M.G. Lagally,editor(s), Solid State Physics: Surfaces. Methods of Experimental Physics, Volume 22.Academic Press, New York, 1985.
171. J.F. Moulder et al. Handbook of X-Ray Photoelectron Spectroscopy. Perkin Elmer, Eden Prairie,MN, 1992.
172. M.H. Kibel. X-Ray Photoelectron Spectroscopy. In D.J. O’Conner, B.A. Sexton, andR.S.C. Smart, editor(s), Surface Analysis Methods in Materials Science. Springer Series inSurface Sciences, Volume 23. Springer-Verlag, Berlin, 1992.
173. K. Robinson and D.J. Tweet. Rep. Prog. Phys. 55:599 (1992).
174. P.H. Fuoss, K.S. Liang, and P. Eisenberger. Grazing-Incidence X-Ray Scattering. InR.Z. Bachrach, editor(s), Synchrotron Radiation Research. Advances in Surface and InterfaceScience, Volume I: Techniques, Plenum Press, New York, 1992.
175. R. Feidenhans’l. Surf. Sci. Rep. 10:105 (1989).
176. F.H.P.M. Habraken, C.M.A.M. Mesters, and G.A. Bootsma. Surf. Sci. 97:264 (1980).
177. R. van Hardeveld and R. Hartog. Surf. Sci. 15:189 (1969).
178. W. Holderich, M. Hesse, and F. Namann. Angew. Chem. (Int. Ed. Engl.). 27:226 (1988).
179. S.M. Csicsery. Shape-Selective Catalysis. In J.A. Rabo, editor(s), Zeolite Chemistry andCatalysis. ACS Monographs, Volume 171. American Chemical Society, Washington, DC, 1976.
180. J.G. Speight. The Chemistry and Technology of Coal. Marcel Dekker, New York, 1983.
REFERENCES 37
181. D.D. Whitehurst, T.O. Mitchell, and M. Farcasiu. Coal Liquefaction: The Chemistry andTechnology of Thermal Process. Academic Press, New York, 1980.
182. C. Klauber. UHV Basics. In D.J. O’Conner, B.A. Sexton, and R.S.C. Smart, editor(s), SurfaceAnalysis Methods in Materials Science. Springer Series in Surface Sciences, Volume 23.Springer-Verlag, Berlin, 1992.
183. J.F. O’Hanlon. A User’s Guide to Vacuum Technique. John Wiley & Sons, Inc., New York, 1989.
184. G.F. Weston. Ultrahigh Vacuum Practice. Butterworths, London, 1985.
185. S. Dushman. Scientific Foundations of Vacuum Technique. John Wiley & Sons, Inc., New York,1962.
186. J.H.d. Boer. The Dynamical Character of Adsorption. Oxford University Press, New York, 1968.
187. F.C. Tompkins. Chemisorption of Gases on Metals. Academic Press, New York, 1978.
188. S.J. Gregg and K.S.W. Sing. Adsorption, Surface Area, and Porosity. Academic Press,New York, 1967.
38 SURFACES: AN INTRODUCTION
