ӕ‫؁‬ᒟ৔ᔈҔፐำ

ଯှ‫݋‬XӀණ৔ૈ᛼‫زࣴޑ‬ᙁϟ

High-Resolution X-ray Scattering Spectroscopy:

Basic Concepts and Case Studies

XӀᙅ৔‫ޑ‬চ౛

Brief of X-ray Scattering and XRD:

Atomic Scattering Factor fa (TO) ,

Structure Factor Fhkl ,
and Bragg Law
 XӀᙅ৔‫ૻޑ‬৲

XӀᙅ৔‫ޑ‬ჴᡍБ‫ݤ‬

ᜳᓂᙟထ፹࿓යٙऱ᧢֏Δ‫ڇ‬࿨ዌՂࠡདྷ௑ൄᑇΕᒕདྷֱ‫ٻ‬Ε࿨དྷၦ
ᄎ‫ࠄڶ‬პऱ᧢೯Δ‫׼‬؆ᝫ‫ڶ‬ฆઌ෗‫ګسٽ‬࿛᧢֏Ζ‫ޗ࣍ط‬றऱࢤᔆፖࠡ࿨
ዌհၴ‫ڶ‬ထയլ‫ױ‬։ऱᣂএΔࢬ‫א‬ઔߒᜳᓂऱ࿨ዌਢᇞ࣫ᜳᓂढࢤऱԫଡ
ૹ૞‫ޡ‬ᨏΖ

ᇞ࣫ᜳᓂ‫ޗ‬ற࿨ዌऱֱऄ‫ڍڶ‬ጟ ‫ݺ‬ଚࠌ‫ش‬ऱֱऄਢ ٠៥୴ऱኔ᧭

ᇞ࣫ᜳᓂ‫ޗ‬ற࿨ዌऱֱऄ‫ڍڶ‬ጟΔ‫ݺ‬ଚࠌ‫ش‬ऱֱऄਢX٠៥୴ऱኔ᧭
‫ݾ‬๬ΖX٠ၞԵᒕདྷ‫ޗ‬றΔᄎࡉདྷ᧯խ଺՗ऱሽ՗ข‫س‬ሽ጖ٌյ‫ش܂‬Δ‫ڼ‬
ᆖ‫଺ط‬՗ཋ୴৵ऱ৬๻ࢤե௫X٠ ‫ܛ‬੡དྷ᧯៥୴ ‫ױ‬൓ࠩᒕདྷ‫ޗ‬றऱ‫ڶ‬
ᆖ‫଺ط‬՗ཋ୴৵ऱ৬๻ࢤե௫X٠Δ‫ܛ‬੡དྷ᧯៥୴Δ‫ױ‬൓ࠩᒕདྷ‫ޗ‬றऱ‫ڶ‬
‫ݧ‬࿨ዌΖൕX٠៥୴ऱൿጒቹᢜ‫אױ‬൓ࠩઌᅝ‫ޗ۞ࠐڍ‬ற࿨ዌऱᇷಛΔࠏ
‫ڕ‬Κ‫ط‬៥୴୽ऱ‫ۯ‬ᆜΔ‫אױ‬ૠጩ‫נ‬དྷ᧯‫ޗ‬றऱདྷ௑ൄᑇΙ‫ط‬៥୴୽ऱ୽ᐈ
‫אױ‬ૠጩ‫ޗ‬றऱৈ‫ٽ‬९৫ (coherence length)ΔࠀԱᇞࠡ࿨དྷࢤऱᚌ‫٭‬Ι‫ڼ‬
؆Δ‫ط‬៥୴୽ऱ୽‫ݮ‬։‫܉‬Δ‫אױ‬Աᇞ‫ޗ‬ற࠹ࠩᚨԺՕ՛ऱ࿓৫Ζ
 XӀᙅ৔‫ޑ‬ჴᡍଛ࿼

‫ء‬ᓰ࿓խտฯऱ˫٠៥୴ኔ᧭๻ໂ੡‫ޡٵ‬ᘿ୴ઔߒխ֨˫٠ኔ᧭৛ᇙऱ
؄ᛩ៥୴ᏚΖჸ಻ၺᄕ᠏ቂ‫ڤ‬ऱ˫٠ᖲΔ‫ڇ‬ԫ౳ᖙ‫פ܂‬෷ ˇˈ˾˩u˅ˈ˃̀˔ հ
ՀΔ‫א‬
Հ ‫ف א‬ᕠ ։٠໢དྷᙇ࠷ ⢸ቂ ᆖሽ՗‫ޔ‬᥮ᚰข‫س‬ऱ ˞E ௽ᐛᘿ୴
௽ᐛᘿ୴Δࠡं
ࠡं
९ O ː ˃ˁˉˆ˅˅ˌÅ Ιࢨਢ‫ޏ‬ང Ꭽቂ ‫˸˚ א‬ʻ˄˄˄ʼ ։٠໢དྷᙇ࠷˄ˁˈˇ˃ˈˉ˅Åऱ˞D˄
௽ᐛᘿ୴Ζ٦ᆖመᐈપ ˃ˁˈ̀̀Ε˃ˁˊ̀̀ ʻࢨ‫ాޓ‬ʼऱࠟิᄷऴ‫ش‬௿ᜓԵ୴۟
ᑌ঴Ζ

˫٠‫ڂ‬ཋ୴ᠦၲདྷ᧯ᑌ঴৵Δᆖመᐈપ
˫٠‫ڂ‬ཋ୴ᠦၲདྷ᧯ᑌ঴৵ ᆖመᐈપ ˄ˁ˄̀̀
˄ ˄̀̀Ε˄̀̀
˄̀̀ ʻࢨ‫ాޓ‬ʼऱ‫ࠟ׼‬
ิᇞ࣫‫ش‬௿ᜓΔ‫˫ط‬٠ೠᛀᕴឯ࠷ൎ৫Ι ˫٠ೠᛀᕴऱൿ༴ᒤ໮‫ױ‬ൕ ˀ˅৫
ࠩˋˇ৫Ζ‫ڇ‬ၦྒྷऱመ࿓խΔኙ࣍ᒕདྷᜳᓂऱᑌ঴ࢬཋ୴‫נ‬ለ೏ऱ៥୴ൎ৫Δ
‫ؘ‬ႊ‫˫ ڇ‬٠ೠᛀᕴ ছ෌ᆜᔞᅝऱൎ৫ಐׂ྇Δ‫א‬ፂ਍ೠᛀᕴऱᒵࢤ᥼ᚨ
֗ࠌ‫ش‬ኂࡎΖ

่඲ᏢҔXӀѤᕉᙅ৔ሺ
 Case Study A. XRD and DAFS

Correlation between Microcrystalline Structure and

Photoluminescence of GaN:Mg Epilayers -

Part I : Structure Characterization

with In-House XRD

Thesis: Chuang, Chin-Pin (NTHU, 2000/06)

Lattice Structure of GaN

the wurtzite lattice the zinc-blende lattice

~ O. Madelung, Data in Science and Technology Semiconductors

Oth th
Other than Group
G IV Elements
El t and
d III
III-V
V Compounds
C d (1992)
 Lattice Structure of GaN

• W
Wurtzite
t it Ph
Phase
( hcp-like)
D phase

• Zinc-Blende
Zinc Blende Phase
( fcc-like)
E phase
h

Stacking Fault between fcc and hcp

 Growth of GaN Film

12 00
m pera ture [ C ] 11 00
10 00 0
0

1075 C
9 00 G aN Ep il ayer
8 00 0
1120 C (depo sitio n rate ~ 1 P m /h r)
7 00
Nitridatio n
6 00
5 00
520 0 C
Tem

4 00 Bu ffer L ayer (40~50 nm )

3 00
2 00
1 00
0
0 2 4 6 8 10 12 14 16 18 20
T im e [ m in ]

Partner’s Study of Interest ...

How to characterize the zinc-blende E-GaN

embedded
b dd d in
i the
h epitaxially
i i ll MOVPE-grown
MOVPE
wurtzite D-GaN ffilms on Al2O3(0001) ?

i e volume fraction of either lattice phase?

i.e.,

samples prepared by Y.C. Pan of NCTU / ElectroPhys. Dept.

ever measured with XRD at NSC Lab in NTHU
 Surface-Normal Radial Scan of GaN:Mg

In-House XRD Characterization - 1

• Radial (2T-T) Scan

– interplane d-spacing Ÿ lattice parameters
– identification of crystalline phase
– quantification of strain and residual stress
2T-T Scan

Radial Scan
 T -Rocking Scan

Configuration of XRD
 Surface-Normal Radial Scan of GaN

GaN:Mg - Radial Scan along Al2O3[0001]

 Radial Scan of Mg-doped GaN: (333), (0006)

4 .0
3 .5 A E x p e rim e n t
F it
3 .0
Intt ens ity
y

2 .5
2 .0
1 .5 B
1 .0
0 .5
0 .0
-0 .5
8 3 .6 8 4 .4 8 5 .2 8 6 .0 8 6 .8 8 7 .6 8 8 .4
2 T [d e g r e e ]
P eak L in e s h a p e Area Am p . C e n te r W i d t h d - s p a c in g
A : V oigt 1 .2 4 5 3 .7 2 8 8 5 .6 5 0 .2 7 5 5 5 .2 1 0
B : V oigt 0 .3
342 1 .0
078 8 6 .0
04 0 .2
2402 5 .1
191

0.04 deg 0.02Å

Radial Scan of Polytyped

y yp GaN Epilayer
p y
 In-House XRD Characterization - 2

• Radial (2T-T) Scan

– interplane d-spacing Ÿ lattice parameters
– identification of crystalline phase
– quantification of strain and residual stress
for in-plane lattice misfit
• Azimuthal (I) Scan & GIXD
– determination of epitaxial relations

Epitaxial D-GaN on Al2O3(0001)

D-GaN {1 0 -1 3}
sity [cps]

4
10
• lattice matching along c-axis 3
10
GaN(0001) // Al2O2 (0001)
Intens

2
10
1
10
0
10
• in-plane orientation relationship Sapphire {1 0 -1 4}

10
5 (10-14) (0-114) (-1104)
10] // Al2O2 [11
ps]

GaN[10-10]
GaN[10 [11-20]
20]
ensity [cp

4
10
3
10
Inte

2
10
1
10
0 60 120 180 240 300 360
I [degree]
 GaN:Mg --- Lattice Matching Relation
4
D - G a N :M g {1 0 - 1 3 }
• S
Samee ass thee U
Undoped
doped GaN
G N 10

Inten siity [cps]

3
10
GaN:Mg(00 0 1),(111) // Al2O2 (0001)

GaN:Mg[10-10],[100] // Al2O2 [11-20]

2
10

1
10

E -G a N :M g {2 0 0 } S a p p h ire {1 1 - 2 6 }
105
5
10
ps]

ps]
4
ensity [cp

10

en sity [cp
4
10
3
10
103
2
10
In te

Inte
2
10 1
10
0
10
101
30 90 15 0 21 0 27 0 33 0 30 90 150 210 270 330
I [d eg re e ] I [d e g re e ]

Resonant X-Ray Scattering Laboratory, National Synchrotron Radiation Research Center

In-Plane Radial Scan along Al2O3[10-10]

H w .r.t. D-A l 2 O 3 (H 0 -H 0) [r.l.u.]

1 2 3 4 5 6
4
10
sub(30-30)

10
3 (11-20)
sub(60-60)
IDet / IMon

2
10 (22-40)
sub(30-30) O /2

1
10

0
10

0.5 1.0 1.5 2.0 2.5

H w.r.t. G aN ((H H -2H 0)) [[r.l.u.]]
 In-House XRD Characterization - 3

• Radial (2T-T) Scan

– interplane d-spacing Ÿ lattice parameters
– identification of crystalline phase
– quantification of strain and residual stress
for in-plane lattice misfit
• Azimuthal (I) Scan & GIXD
– determination of epitaxial relations

• Pole
P l Fi
Figure
– distribution of orientation

Surface-Normal Radial Scan of GaN:Mg

Polar Scan of (10-11)-Defect Structures

Cp2Mg%

Pole Figure of GaN(10-11)

 Short Summary - 1

• GaN:Mg
G N: g layers
ye s aree we
well g
grown
ow us
usingg MOVPE;
OV ; thee average
ve ge
grain size exceeds 0.3 Pm and mosaic is better than 0.2 deg.
Magnesium can reduce the stacking energy difference
between wurtzite and zinc-blende structures so as to make
coexistence of two phases at high growth temperatures .
• The d-spacing difference between D-GaN (0002) and E-
GaN (111) is about 0.02 Å, which can be resolved with the
conventional in-house XRD measurements.
• Two q
questions are g
generated thereafter:
– Peak assignment of polytyped (0 0 0 2n) and (n n n) diffraction?
– Origin & implications of the preferred (1 0 -1 1) textures?

Short Summary - 2

• With much increasing flow rate of Cp2Mg, the role of Mg

ions changes from the p-typed dopant to nucleation center,
which generates the prismatic step fronts and thus inverse
d
domaini boundaries.
b d i
• These Mg-rich defect phases of 8.40-tilted (10-11) orientation
are coherent to the substitutional-interstitial model of Mg-
complexes and well correlate to the prevailing of yellow band
in PL spectra.
spectra
• DAFS directly resolves the essential properties obscured in
the mixed phase of GaN:Mg films,
films down to the sensitivity
of sub-micron meters.