3 材料化學晶體與電子結構劉如熹 0924 2020

台灣大學化學系．材料化學實驗室
Materials Chemistry Laboratory

Department of Chemistry
National Taiwan University
材料化學-晶體與電子結構
任課教師: 劉如熹 (臺灣大學化學系)
材料化學-晶體與電子結構 1/246
內容
X-ray Crystallography
Powder X-ray Diffraction
X-ray Absorption and Applications
X-ray Crystallography
Unit cell
Symmetry (point and space symmetries)
Crystal system and Bravais lattice
230 space group
Meaning of the space group
Unit cell
Unit cell
The smallest repeating unit which shows
the full symmetry of the crystal structure
Regular arrangements of the atoms in three dimensions

[There are translation vectors (i.e. translation symmetry) to generate the atoms.]
Build up
Crystal
Symmetry
Point symmetry
Space symmetry
Point symmetry (點對稱)

Rotational symmetry (旋轉對稱)
Reflectional symmetry（反射對稱)
Inversive symmetry (反逆對稱)
Rotational and inversive symmetry (反轉對稱)
Rotational symmetry (旋轉對稱)
Rotation axis (旋轉軸); n

旋轉對稱是繞著一根通過中心點
的軸做定量旋轉的運動；該軸可
稱為旋轉軸（Rotation axis），如
右圖旋轉的角度則為φ；當結晶具
有旋轉對稱時，須符合旋轉後晶
格能再次重合，而n重旋轉軸（n-
fold axis）表經由n次旋轉後晶格
恢復至原來之位置。
旋轉（ψ角）對稱示意圖
Symmetry with respect to an axis
Rotation about the axis by 360/n
n=1 n=2 n=3 n=4 n=6
五種旋轉對稱圖與其代表符號
Pentagons (x) Hexagons (o)
（五重對稱性不能被晶體作為一個整體）
Translation（直移）：原子在空間之重覆規則出現，
可以經由這直移向量之位移
而得到
Translation symmetry operation

• t ：為A、B兩晶格點直移向量

• P、A、B、M為沿 t 方向之連續
四晶格點
Q mt N
• A、B旋轉軸分別將P、M經α角
度旋轉至Q、N
t t
• 根據直移對稱 α α
QN = mt （m為整數）……
P C A t B D M
但QN = (CA+AB+BD)
∴QN = t cosα+ t + t cosα…
將 代入
mt = t (2cosα + 1)
∴m-1 = 2cosα
m 1
cosα = 2 m = 3, cosα = 1 ∴ α = 0 or 360°(1-fold)
1
∵ -1≦ cosα≦ 1 m = 2, cosα = 2 ∴ α = 60°(6-fold) （六重軸）
m 1
∴ -1≦ 2 ≦ 1 m = 1, cosα = 0 ∴ α = 90°(4-fold) （四重軸）
1
-2≦ m-1≦ 2 m = 0, cosα =  2 ∴ α = 120°(3-fold)
-1≦ m ≦ 3 m = -1, cosα = -1 ∴ α = 180°(2-fold)
Reflectional symmetry (反射對稱)
Mirror plane (鏡面）; m
反射是指對一鏡面m的對稱反覆運動。
如左圖，一通過格子點O垂直紙面的鏡
面m，鏡面的反射關係如圖上箭號所示。
(Symmetry respect to a plane)

反射對稱
Inversive symmetry (反逆對稱)
Center of symmetry (對稱中心); 1

對稱中心，是對一個點做反覆對
稱的對稱方式。如圖所示，I為對
稱中心(Symmetry center)，亦稱反
逆中心 ( I n v e r s i o n
Center)。
對稱中心
Rotational and inversive symmetry
(反轉對稱)
Inversion axis (反軸); n
將旋轉與反逆結合，形成一種混合式的
對稱運動稱為反轉(旋逆)對稱，而其旋
轉軸則稱為反軸(Inversion axis)。以圖為
例：首先須先繞n=2的旋轉軸旋轉由1至
2，第二步通過I對稱至3的位置;由此可
見所謂的即為旋轉與反逆對稱運動
的結合。
2 示意圖
Point symmetry 之特性

進行對稱操作時，至少有一點不動
(即若一個原子位於對稱中心、旋轉軸或鏡面上時，
當進行各自目的對稱操作時，此原子保持不動。)
32個點群
將四種點對稱取一種或一種以上組合
可得32個不同之對稱群，每一對稱群之對稱元素皆交會於一點，
此即為晶體外形多面體之中心點。
此32個對稱群又稱為32 point group。
任何一結晶物質若出現完整之幾何外形時，則其結晶外觀對稱必定屬於
此32個點群對稱中之一。
32 point group 代表32類不同之結晶幾何外觀對稱
一個點群代表一個晶類的對稱性
Materials Chemistry Laboratory Comparison of Hermann-Mauguin and
National Taiwan University SchÖ nflies notations for 32 point group
1 2 3 4 6 Hermann-Mauguin notation (crystallography)
(C1) (C2) (C3) (C4) (C6) Schonflies notation (spectroscopy)
1 2 =m 3 4 6 = 3/m
(Ci) (Cs) (C3i) (S4) (C3h)
(222) (32) (422) (622) (23) (432)
(D2) (D3) (D4) (D6) (T) (O)
(mm2) (3m) (4mm) (6mm)
(C2v) (C3v) (C4v) (C6v)
(mmm)( 6 m2)(4/mmm)(6/mmm) (m3) (m3m)
(D2h) (D3h) (D4h) (D6h) (Th) (Oh)
( 4 2m) ( 3 m) ( 4 3m)
(D2d) (D3d) (Td)
(2/m) (4/m) (6/m)
(C2h) (C4h) (C6h)
正方體4mm示意圖正方體4/mmm示意圖
Space symmetry (空間對稱)

Crystal with their infinite repeating structures
Screw axis
Glide plane
Screw axis (旋移軸)

Combine rotation and translation
XY : Rotation 360/X about the screw axis
Translation Y/X of the unit cell edge in the

direction of the screw axis
二重旋移軸
Glide plane (射移面)

Combine translation and reflection
(A glide plane is a translation followed by a reflection in a plane parallel to the translation axis)
a
b (射移面之方位)
a-glide plane
不同種類之glide plane
射移面名稱符號直移射移面之方位
axial glide a a/2 [010] [001]

(晶軸射移) b b/2 [100] [001]
c c/2 [100] [010]
diagonal glide n (a+b)/2 [001]

(斜角射移) n (b+c)/2 [100]
n (c+a)/2 [010]
diamond glide d (a+b)/4 [001]

(鑽石射移) d (b+c)/4 [100]
d (c+a)/4 [010]
Crystal system and

Bravais lattice
Definition of axes, unit cell dimensions and angles for a general

z
c
 b

a  y
Department of Chemistry Cubic
Cubic Unit cell Characteristic symmetry

（立方晶系）
（正方或等軸晶系） a=b=c
Four threefold axes
Α = β= γ = 90°
n=3
n=4
n=3 ※先有characteristic
sym. ，才有unit cell的
條件。而不是先有
n=2 unit cell條件，才有
characteristic sym.
Tetragonal
Tetragonal Unit cell Characteristic symmetry

(正方晶系)
a=b≠c
One fourfold axis
 = β =γ = 90°
n=4
Orthorhombic
Orthorhombic Unit cell Characteristic symmetry

(斜方晶系)(長方晶系)
a≠b≠c twofold axes in three mutually
 = β = γ = 90° perpendicular direction
n=2
Hexagonal
Hexagonal Unit cell Characteristic symmetry

（六方晶系）
a=b≠c
One sixfold axis
 = β = 90° , γ = 120°
n=6
Trigonal
Trigonal (Rhombohedral) Unit cell Characteristic symmetry
（三方晶系；菱形晶系） a=b=c One threefold axis

α = β = γ  90°
n=3
n=3
Deviation of a trigonal
unit cell from a cubic cell
Monoclinic
Monoclinic Unit cell Characteristic symmetry

（單斜晶系）
a≠b≠c
 = γ = 90°, β ≠ 90° One twofold axis
m
National Taiwan University Triclinic
Triclinic Unit cell Characteristic symmetry

（三斜晶系）
a≠b≠c 1-fold (identity or inversion)
α ≠ β ≠ γ ≠ 90° symmetry only
七種晶體體系(Crystal system)
National Taiwan University 7種晶體體系
體系晶軸與晶角 Essential
symmetry
Cubic a = b = c,α=β=γ=900 Four threefold
axes
0
Tetragonal a = b≠c,α=β=γ=90 One fourfold axis
0
Orthorhombic a≠b≠c,α=β=γ=90 Three twofold
axes or
Mirror planes
Hexagonal a = b≠c,α=β=900γ=1200 One sixfold axis
Trigonal a = b = c,α=β=γ≠900 One threefold

axis
0
Monoclinic a≠b≠c,α=γ=90 ≠β One twofold axis
or
mirror plane
0
Triclinic a≠b≠c,α≠β≠γ≠90 none
Lattice (晶格)
用點的排列表示晶體中原子、分子或離子的重覆方式
四種晶格（Lattices）
原始晶格; P 體心晶格; I 面心晶格; F 邊心晶格; (C, A, B)

(Primitive unit cell) （Body centered unit cell）
（Face centered unit cell）
（Side centered unit cell）
National Taiwan University International system
National Taiwan University Bravais Lattice
Bravais Lattice
‧seven crystal systems
14 Bravais lattices
‧four types of lattice
法國結晶學家 Auguste Bravais
透過4種三度空間的晶格與7種晶體體系組合出下列14
種Bravais Lattice晶格
體系晶軸與晶角 Bravais 晶格
0
Cubic a = b = c,α=β=γ=90 P,I,F
0
Tetragonal a = b≠c,α=β=γ=90 P,I
0
Orthorhombic a≠b≠c,α=β=γ=90 P,I,C,F
0
Trigonal a = b = c,α=β=γ≠90 R
0 0
Hexagonal a = b≠c,α=β=90 γ=120 P
0
Monoclinic a≠b≠c,α=γ=90 ≠β P,C
0
Triclinic a≠b≠c,α≠β≠γ≠90 P
230 space group
4-type of point symmetries (10 elements)
32 point groups (只是描述結晶之幾何外觀對稱)

+
14 Bravais Lattice (只描述translation)
73 space group (Lattice)

形成73種空間群後，透過晶格
+ 的旋移（Screw）和射移(glide)
Screw, glide
，將原本只能平移的空間群，
變得可以旋移和射移，而組合
出完整的230種空間群。
230 actual space group
(可查international Tables for crystallography一書之第一卷)
Meaning of the
space group
Space group symbol
(a) for Tetragonal, Hexagonal and Trigonal
(含68個空間群) (含27個空間群) (含25個空間群)
L S1 S2 S3
Lattice type (eg, P, I,….)

[001] (與c軸方向一致或垂直的對稱元素)
[100]或[010] (與a軸或b軸一致或垂直的對稱元素)
與[110]或[1-10]方向一致或垂直的對稱元素(Tetragonal)
與[210]方向一致或垂直的對稱元素(Hexagonal, Trigonal)
n = 4 eg.Tetragonal (TlBa2Can-1CunO2n+3, n = 1, 2, 3, 4)
mab
P 4/m m m
c mb
晶格屬primitive之tetragonal晶格
ma
mc 表沿c軸方向有4重旋轉軸,且垂直於該方向為反射面(mc)
b
a
表垂直a軸或b軸方向有反射面 (ma, mb)
表ab面diagonal有反射面(mab)
(b) For orthorhombic (含59個空間群）

L S1 S2 S3
Lattice type
a方向最高的對稱元素
b方向最高的對稱元素
c方向最高的對稱元素
eg. orthorhombic
P b a 2
表示其晶格為primitive之orthorhombic晶格
垂直a方向為b軸之射移面
垂直b方向為a軸之射移面
沿c軸方向為二重旋轉軸
(c) For Cubic (含36個空間群）

L S1 S2 S3
Lattice type
沿a軸（或b或c）一致或垂直之對稱元素
沿[111]方向（或[1-11]或[-111]），方向一致或垂直之對稱元素
沿[110]方向（或[-110]或[1-10]），方向一致或垂直之對稱元素
eg. cubic
I 41/a 3 2/d
表示其晶格為body-center之cubic晶格
沿c軸方向有41旋移軸，垂直c方向有
a軸之glide plane
沿[111]方向有3重旋逆軸
沿[110]方向有2重旋轉軸，垂直為[110]方向
有d (diamond) glide plane
(d) For Monclinic (含13個空間群）

L S1 S2 S3
(X) (X)
Lattice type
沿a軸或b軸之對稱元素
eg. monoclinic
C 2/m
c邊心之monoclinic晶格
沿b軸方向為二重旋轉軸，而垂直於該方向為反射面
(e) For Triclinic (含2個空間群）
P ，
1 P1
毫無對稱元素
僅具對稱心
Powder X-ray Diffraction
Miller indices
d-spacing formulae
Systematically absent reflection
X-ray generation
Diffraction
Rietveld analysis of crystal structure
by powder X-ray diffraction
Lattice planes, Miller indices,

d-spacing and systematically
absent reflection
Lattice Planes
d2
d3
d1
此些晶格點排列可分成許多不同行列的組，
每一組內相鄰的兩列之間都有一特徵之垂直距離d
於三維情況中，此些行列變成平面，
相鄰平面間距為面間距d
Miller Indices (米勒指數)
Lattices planes are labeled by assigning three numbers
known a Miller Indices to each set.
z
(hkl) ※a, b, c – lattice parameters
lc
c
Where h = a/la ※If la, lb, orlc is a minus
la k = b/lb number, a “—“ must be
lb x
a l = c/lc added on the number in
y b Miller Indices.
※h, k, l must be integrals.
eg.1 c
eg.2
原點 a
b -a -a/2 a/2 a
la=1/2a b/2
lb=1/2b (hkl) = (221) b All of them are
lc=c (220 ) planes
Miller indices of planes in hexagonal crystals (h k i l)

c
h+k+i=0
a3
-1(h) ≡( 1 2.0)
≡( 1 20)
a2
a1
-1(i) 1/2(k)
Directions in crystal
<100> sets of directions are equivalent

e.g Cubic [100] [010] = <100>
National Taiwan University d – spacing formula
1 h2  k 2  l 2
• Cubic 2

d a2
For (100) planes → d = a
2d sin    For (200) palnes → d = a/2

d
2 sin 
測量得d，即可知a
• Orthorhombic
1 h2 k 2 l 2
2
 2 2 2
d a b c
• Tetragonal
1 h2 k 2 l 2
2
 2
 2 （∵a = b）
d a c
National Taiwan University Systematically absent reflections
Lattice type Rule for reflection to be

observed
P (Primitive) None
I (Body centered) h +k +l = 2 n
F (Face centered) h ,k ,l either all odd or all
even
C (Side centered) h +k = 2 n
R (Rhombohedral) - h +k +l = 3 n
(or h -k +l = 3 n)
eg. -Fe: body centered cubic
所有的原子均位於(200)面，沒有原子
處於(200)面之間而造成相消干涉
體心原子位於相鄰(100)面間的中途，其繞射的X射線相對於(100)面上頂角上
的原子繞射，恰巧有180o 的相位差對整個晶體平均起來，有相等數目的體心
原子和頂角上的原子故而他們的繞射束完全互相對消。
X-ray generation,
Diffraction and
Rietveld analysis
(Monochromatic)
Generation of Cu Kα X-rays. A 2p electron falls into the empty

1s level (□ ) and the excess energy is released as X-rays.
3D5/2 MⅤ
3d{3D3/2 MⅣ
3P3/2
3p{3P1/2 MⅢ
MⅡ
3s 3S1/2
MⅠ
原子中電子游離之X光譜能階
殼層 1s 2s 2p 3s 3p 3d
2P3/2 移去 1S1/2 2S1/2 2P1/2 3S1/2 3P1/2 3P3/2

LⅢ 電子 2P3/2 3D3/2 3D5/2
2p{ 2P1/2 LⅡ 層位
2S1/2
2s LⅠ
}
X- K LⅠ LⅡ MⅠ MⅡ MⅢ MⅣ
L 射線 LⅢ MⅤ
Kα2 Kα1 態
Selection rule:
Δl = ±1
1S1/2
1s K
}
Kα Kβ
2p 1s 3p 1s
White radiation:
高能荷電粒子(30,000V)與物質碰撞時,
就產生X射線。由於碰撞，電子被減速
或停止運動，其失去能量的一部份轉
變成電磁輻射，此過程給出波長範圍
在某一下限值以上的 “white radiation”
X-rays。
λmin(Å ) = 12400/V
V: accelerating voltage
X-ray emission spectrum of a metal,

e.g. copper
連續光譜
以高電壓加速的電子束撞擊陽極靶標，高速電子受靶標原子
的阻檔而急遽停止，以此方法產生的X光與靶標原子之特性無
關，是以連續性不同波長同時出現，也稱白光光譜。
特性輻射光譜
也是以高速電子撞到靶標原子，但不同的是，高速電子將能量傳
給原子中的電子，使原子內層軌域的電子被激發，隨之外層電子
躍遷到空出的內層軌域位置，因不同軌域的能階差放出X光，此X
光和原子種類有關，稱為特性輻射(Characteristic Spectrum)。
繞射現象視為入射光被晶面反射，如同鏡面反射一樣，
入射角等於反射角，當光程差為波長的整數倍時，呈
現加強效應，產生建設性干涉，光程差不是波長的整
數倍時，視為削減效應，故繞射峰只在特定的θ發生。
Bragg’s law : 2 d sin θ = n λ

X-rays (e.g. Cu Kα , λ= 1.54Å)
θθ d
dsinθ
Braggs’ Law
2dhklsinθ=nλ
dhkl：平行面中兩鄰近面間的距離
θ ：入射光和平面的夾角
λ：入射光的波長
晶胞內組成原子不同時，由於各原子對X光的散射相異，故雖結
構相同可能有不同的繞射強度。
故X光繞射實驗提供：
(1)繞射峰的位置2θ：晶格參數，晶胞大小
(2)繞射峰的強度I：晶體組成原子種類及位置的資料
必須滿足下列二個條件：
(1)入射光、繞射光與晶體平行面之法線在同一平面
(2)入射角等於反射角。
(avoid collisions between air particles and

anode（陽極） either the incident electrons or emitted X-rays)
極小部分 → X-ray
大部分 → 熱
30 kV
4Be
X光管
兩種不同之旋轉陽極
Department of Chemistry K absorption edge = 1.4881Å
for Ni
Cu Cu / Ni filter (The energy required to ionize

Mass Absorption Coefficient
Kα
1s electrons for Ni)
X-ray Intensity
Ni foil is effective in
Kα absorbing the Cu Kβ
radiation and most of the
Kβ
white radiation, leaving a
monochromatic, resonably
clean beam of Kα radiation.
Kβ
λ (Å) λ (Å)
(a) No filter (b) Nickel filter
Fig comparison of the spectra of copper radiation (a) before (b) after passage through a
nickel filter (schematic). The dashed line is the mass absorption coefficient of nickel
Table Filter for the Production of Monochromatic X-rays

Thickness in Kβ
λ of Kα Absorbed
Target Doublet(Å ) Filter mma Milsb Grams/cm2 (percent)
Ag 0.561 Pd 0.0461 1.8 0.0056 96.0
Rh 0.0480 1.9 0.060 96.4
Mo 0.711 Nb 0.0431 1.9 0.040 96.5
Zr 0.0673 2.7 0.044 96.8

Cu 1.542 Ni 0.0170 0.7 0.015 98.4
Ni 1.659 Co 0.0158 0.6 0.014 98.7
Co 1.790 Fe 0.0166 0.7 0.013 98.9

Fe 1.937 Mn 0.0163 0.7 0.012 99.2
Cr 2.291 V 0.0169 0.7 0.010 99.4
a Thickness given reduces Kα radiation by 50 percent
b1 Mil = 0.001 in
Table X-ray Wavelength Most Useful in Diffraction Studiesa
K Excitation
Unresolvedb Absorption Potential
Element Kα1(Å ) Kα2(Å ) Kα(Å ) Kβ1 (Å ) Edge(Å ) (kV)
Ag 0.55941 0.56380 0.56084 0.49707 0.4859 25.52
Mo 0.70930 0.71359 0.71073 0.63229 0.6198 20.00
Cu 1.54056 1.54439 1.54184 1.39222 1.3806 3.98
Ni 1.65791 1.66175 1.65919 1.50014 1.4831 8.33
Co 1.78897 1.79285 1.79026 1.62079 1.6082 7.71
Fe 1.93604 1.93998 1.93735 1.75661 1.7435 7.11
Cr 2.23970 2.29361 2.29100 2.08487 2.0702 5.99
aThese values are taken from Bearden[43] in which they were lived on a readjusted scale of Å units
based on λ(W Kα1) = 0.2090100 Å .Since 1 Å = 1Å to + 5ppm (probable error). Values in this table
are designated as being in angstrom units.
bThese values are the customary weighted mean of Kα and Kα , Kα being given twice the weight
1 2 1
of Kα1
XRD 儀器介紹
1. 光源（Source）
2. 角度儀（Goniometer）
3. 偵測器（Detector）
4. 套裝系統
光源
- X光管（X-ray tube）
- 單光器（monochromater）
- 準直器（Collimator）
National Taiwan University X光管（X-ray tube）
旋轉陽極式
密封式 (Rotating anode)
Ref: 1. www.nonius.com
2. www.rigaku.com
單光器（monochromater）
Ref: www.scintag.com
準直器（Collimator）
角度儀（Goniometer）
(For single crystal)
Ref: www.nonius.com
National Taiwan University 偵測器
1. 攝影底片單層乳劑負片
（photographic films）雙層乳劑負片
拍立得正片(polaroid films)
2. 離子化偵測器離子化室(ionization chamber)
（ionization detectors）比例計數器
G-M計數器(Geiger-Muller
counter)
3. 固態偵測器螢光幕(fluorescent screens)
（solid state detectors）閃爍計數器
半導體計數器
Ref: 吳泰伯; 許樹恩, X光繞射原理與材料結構分析(1992)

影像感光版
（image plate）
Ref: www.rigaku.com
比例計數器（proportional counter）
操作電壓： 800～1000V
光子產生之脈動可放大500～10000倍
Ref: SKOOG; LEARY, Analytical Chemistry, 4th Edition,1991
閃爍計數器（scientillation）
NaI + TlI2(0.2%)
粉末繞射儀（Powder XRD）
National Taiwan University 偵檢器
光源
數據收集
A 樣品
1. 反射式:(圖A)
光源入射角與反射角相同, 具para-focusing, 訊偵檢器
號強度較穿透式強, 但在低角度時所得訊號會光源
樣品
下降, 且此法不適用於低吸收係數之樣品; 故
多用於量測高吸收係數樣品於較高角度之光 B
譜.
偵檢器
2. 穿透式: (圖B, C) 光源
樣品
分為Normal-beam穿透式(B) 及對稱穿透式(C)
兩種, 訊號強度較反射式為低, 但可適用低吸 C
收係數樣品, 且可進行低角度之分析(2 =
0.2°~1.0°). 此法多用於有機物質之分析.
反射式及穿透式兩種方法所得之光譜比較可
用來鑑定雜相之存在及繞射強度之變化.
Ref: X-ray Diffraction Procedures (1974).
BaTiO3
Ba
Ti
XRD
Cubic; space group: Pm-3m

a=4Å
Intensity
BaTiO3 JCPDS
Sys:Tetragonal S.G.:P4mm
20 30 40 50 60
Two theta
X-ray source X-ray detector
(X-ray tube)
X-rays (e.g. Cu Kα , λ= 1.5418 Å)
θ θ
θθ d
“同步移動”
dsinθ 光程差
X-ray source Bragg’s law 2 d sin θ = n λ

(X-ray tube) X-ray detector
Sample holder
National Taiwan University YBa 2 Cu 3 O 7 (TC = 90 K)
(103) (110)
Intensity
(013)
(005) (014)(104)
Miller index plane
(006) (020)
(116)
(012)(102)
(113)
(016)(023)
(007)(122)
(003)
(200)
(213)
(018)
(026)
(112)
(115)
(002)
(205)
(025)
(117)
5 10 15 20 25 30 35 40 45 50 55 60 65 70
2 - Theta
如何得到(hkl)值： 2d sin   n (λ= 1.5418 Å for Cu Kα)
（θ改變 → 得到不同組的dhkl）
National Taiwan University Indexing of Peaks (hkl)
2dhklsinθ = λ = 1.5418 Å
 d = λ/2sinθ (θ由Exp 獲得）
hkl
 get d , d , d ………
1 2 3
For cubic system
1 h2 k2 l2 1
2
 2  2  2  2 (h 2  k 2  l 2 )
d hkl a b c a
1 1
2
 2
(h 2
1  k 2
1  l1
2
) ................. (1)
d1 a
1 1
2
 2
(h 2
2  k 2
2  l 2
2 ) ................. (2)
d2 a
................
1 1
2
 2
(h 2n  k 2n  l 2n ) .................. (n)
dn a
After least square refinement
get a (晶格常數）
 h1,k1,l1
h2,k2,l2 …..hn,kn,ln
Department of Chemistry Table Formulas Calculating Interplanar Spacings dhkl
•System Axial Axial Angles d hkl

Translations
•1.Cubic a=b=c α=β=γ=90o a(h2+k2+l2)-1/2
•2.Tetragonal a=b≠c α=β=γ=90o [(h2/a2)+(k2/a2)+(l2/c2)]-1/2
•3.Orthorhombic a≠b≠c α=β=γ=90o [(h2/a2)+(k2/b2)+(l2/c2)]-1/2
•4.(A)Hexagonal a=b≠c α=β=90o, γ=120o [(4/3a2) (h2+k2+hk)+(l2/c2)]-1/2
(B)Rhombohedral a=b=c α=β=γ=90o＜120o a[(h2+k2+l2)sin2α+2(hk+hl+kl)(cos2α-
cosα)/1+2cos2α3+2cos2α]-1/2
•5.Monoclinic a≠b≠c α=γ=90o , β＞90o [(h2/a2)+ (l2/c2)(2hl/ac)cosβ/sin2+k2/b2]-1/2

-1/2
•6.Triclinic a≠b≠c α≠β≠γ ≠90o
National Taiwan University Intensity of XRD pattern
I hkl  k Fhkl Phkl LPe  m
2
eix= cosx + isinx
Fhkl   Pn f n exp 2ihX n  kYn  lZ n 
1  Cos 2 2 The scattered beams are most intense when parallel and
LP  anti-parallel to the incident beam and are weakest when
Sin 2Cos at 90 ° to the incident beam.
其中 k 為比例常數(scale factor)
Fhkl 為hkl晶面的結構因子(structure factor)
Phkl 為hkl晶面的multiplicity（多重性)
LP 為Lorentz-polarization factor, 為一角度的函數
e-m 為溫度係數(temperature factor)
Pn 為原子n在(Xn, Yn, Zn)位置的占有率(occupancy)
fn 為原子的散射因子(atomic scattering factor; form factor)
h, k, l 為繞射晶面的Miller indices
Xn, Yn, Zn 為原子在單位晶胞中的座標
Form factor, fn , (scattering factor)

Z (atomic number  the number of electrons possessed by that atom)
輕原子很難以x-ray定位
(e.g. H)(須以neutron；
乃因中子散射因子不是
原子序數的簡單函數)
許多物質的powder x-ray
在高角度(2θ>60°-70°)
其intensity降低許多
Form factor of Ca2+ and F-
Materials Chemistry Laboratory e.g. Fhkl = fnexp2πi(hXn+kYn+lZn)
= fn(cos2π(hXn+kYn+lZn)+isin2π(hXn+kYn+lZn)
CaF2 fluorite structure (face centered cubic)

Ca (0, 0, 0) (1/2, 1/2, 0) (1/2, 0, 1/2) (0, 1/2, 1/2)
F (1/4, 1/4, 1/4) (1/4, 1/4, 3/4) (1/4, 3/4, 1/4)
(3/4, 1/4, 1/4) (3/4, 3/4, 1/4) (3/4, 1/4, 3/4)
(1/4, 3/4, 3/4) (3/4, 3/4, 3/4)
The fluorite (螢石) structure (CaF2)
CN for Ca2+ = 8; CN for F- = 4
cubic: Fm3m
Ca
e.g. Fhkl = fnexp2πi(hXn+kYn+lZn)
National Taiwan University = fn(cos2π(hXn+kYn+lZn)+isin2π(hXn+kYn+lZn)
CaF2 fluorite structure (face centered cubic)

Ca (0, 0, 0) (1/2, 1/2, 0) (1/2, 0, 1/2) (0, 1/2, 1/2)
F (1/4, 1/4, 1/4) (1/4, 1/4, 3/4) (1/4, 3/4, 1/4)
(3/4, 1/4, 1/4) (3/4, 3/4, 1/4) (3/4, 1/4, 3/4)
(1/4, 3/4, 3/4) (3/4, 3/4, 3/4)
Fhkl = fCa[cos2π(0)+cosπ(h+k)+cosπ(h+l)+
cosπ(k+l)]+ifCa[sin2π(0)+sinπ(h+k)+sinπ(h+l)+sinπ(k+l)]
+fF [cosπ/2(h+k+l)+cosπ/2(h+k+3l)
+cosπ/2(h+3k+l)+cosπ/2(3h+k+l)
+cosπ/2(3h+3k+l)+cosπ/2(3h+k+3l)
+cosπ/2(h+3k+3l)+cosπ/2(3h+3k+3l)]
+ifF [sinπ/2(h+k+l)+sinπ/2(h+k+3l)
+sinπ/2(h+3k+l)+sinπ/2(3h+k+l)
+sinπ/2(3h+3k+l)+sinπ/2(3h+k+3l)
+sinπ/2(h+3k+3l)+sinπ/2(3h+3k+3l)]
F202 = fCa(cos0+cos2π+cos4π+cos2π)+
ifCa(sin0+sin2π+sin4π+sin2π)
+fF(cos2π+cos4π+cos2π+cos4π+cos4π
+cos6π+cos4π+cos6π)
+ ifF(sin2π+sin4π+sin2π+sin4π+sin4π
+sin6π+sin4π+sin6π)
F202= fCa(1+1+1+1)+ifCa(0+0+0+0)
+fF(1+1+1+1+1+1+1+1)+ifF(0+0+0+0+0+0+0+0)
F202=4fCa+8fF
the 202 reflection in CaF2 has a d-spacing
of 1.929Å (a = 5.464Å)
2d202sinθ = nλ (λ = 1.5418Å for Cu Kα)
θ202 = sin-11.5418/2x1.929 = 23.6o
sin θ/ λ = 0.259 fCa=12.65 fF=5.8
F202 = 4x12.65+8x5.8 = 97
Since the fluorite structure is face centered cubic,

h, k, and l must be either all odd or all even for an
observed reflection; for any other combination,
F = 0 (try it!)
e.g. F102 = 0
Fhklcal  calculated structure factors

Fhklobs  observed structure factors
R(residual factor) = ||Fobs|- |Fcal|| (R-factor)
 |Fobs|
最初原始模型?
原始數據溫度係數
I obs 佔有率表 Rietveld 法解析流程
●Rietveld structure refinement
for powder x-ray diffraction
波形函數
背景值校正
pattern
晶格常數 ●step scan → peak intensity
(1) 每個step的間距：
0.02°
I calc
(2) 每個step的計數時間：
8 sec/step
(3) 角度：20 °~ 130°
最小平方誤差法 (2θ)
electron 粗糙原子模型
density map
精確原子模型
Rp、Rwp、鍵長、鍵角
Department of Chemistry 利用最小平方誤差法使下式的x為最小值
x   Wi (Yi ( obs )  Yi ( calc ) ) 2

Wi 為權值, Wi =1/Yi(obs)
Yi(obs)為step scan中第i個step收集到的強度
Yi(calc)為第i個理論計算強度的點,它是將此點上所有
鄰近Bragg繞射的強度再加上背景值而得到的，Yi(calc)
可表示為下式：
Yi ( calc )   A @  mhkl LP Fhkl  p (2 l  2 hkl ) Phkl  Ylb
2
原子位置
其中＠為樣品中的組成數目(phase number) 占有率
A 為比例參數(scale factor) 晶格常數
mhkl 為hkl晶面的multiplicity（多重性) 溫度係數
LP 為Lorentz-polarization factor, 為一角度的函數 Isotropic temperature factor; B
Anisotropic temperature factor;
Fhkl 為hkl晶面的結構因子(structure factor)
B11, B22, B33, B12, B13, B23
Φ 為波形函數(the reflection profile function which approximates

the effects of both instrumental and ,possibly, specimen features)
Phkl 為優向排列(prefer orientation)函數
Ylb 為背景值
結構解析後所得到可信值定義為R-Bragg、R-pattern與R-weighted pattern
R 
 I I '
o c

b '
I o
(R-Bragg)
RP 
 Y Y i .o i .c
Y i .o
(R-pattern)
  Wi (Yi.o  Yi.c ) 2 
1/ 2
RWP  
  Wi Yi.o 
2

(R-weighted pattern)
Fig. The observed (dotted line), calculated (solid line) and difference
powder X-ray diffraction patterns of the sample with a nominal
Composition of (Pb0.5Hg0.5)(Sr1.2La0.8)CuO5-δ
Table
Positionala, thermal parameters B(Å 2) and site occupancies(g) of the
Sample having the nominal composition (Pb0.5Hg0.5)(Sr1.2La0.8)CuO5
Tetragonal
Atom Site x y z B g
(Pb/Hg) 1a 0 0 0 0.5 0.5/0.5
(Sr/La) 2h 0.5 0.5 0.2821(3) 0.5 0.6/0.4
Cu 1b 0 0 0.5 0.5 1.0
O(1) 2e 0 0.5 0.5 1.0 1.0
O(2) 2g 0 0 0.269(5) 1.0 1.0
O(3)b 4n 0.33(2) 0.5 0 1.0 1.0
a=3.7908(2)Å
c=8.6915(6)Å
Rp=9.35%
Rwp=14.36%
1. Space group P4/mmm (No. 123).

2. Refined off ideal site from 1c to 4n.
Table
Selected interatomic distances (Å ) for the compound having the
nominal composition of (Pb0.5Hg0.5)(Sr1.2La0.8)CuO5. K is the
number of equivalent bonds.
Bonds Distances(Å ) K
Pb/Hg -O(2) 2.34(4) 2
-O(3) 2.27(4) 8
-O(3) 3.18(6) 8
Sr/La -O(1) 2.679(2) 4
-O(2) 2.683(2) 4
-O(3) 2.54(2) 4
Cu -O(1) 1.815 4
-O(2) 2.01(4) 2
National Taiwan University (Pb0.5Hg0.5)(Sr1.2La0.8)CuO5-δ
P4/mmm (Tetragonal)
2.01Å
c=8.69Å
Materials Chemistry Laboratory [010] SAED
Fig. A typical [010] SAED pattern (inset) and HREM image of the sample (Pb0.5Hg0.5)(Sr1.2La0.8)CuO5-δ
(Selected area electron diffraction) (High resolution electron microscope)
National Taiwan University Solid State Reaction
XRD Patterns of (Y3-xCex)Al5O12
x x
x = 0.3
Intensity
x x
x = 0.2
x
x = 0.1
x = 0.07
x
x = 0.05
(532)
(211)
(642)
(640)
(400)
(444)
(321)
(521)
(422)
(420)
(220)
(431)
(440)
(552)
(631)
x=0
10 20 30 40 50 60
2θ
XRD Refinement of (Y3-xCex)Al5O12 with x = 0.07
Crystallographic data for (Y2.93Ce0.07)Al5O12
Atoms x y z Fraction Uiso

Ce 0.125 0 0.25 0.023 0.0164 (2)
Y 0.125 0 0.25 0.977 0.0164 (2)
Al 0 0 0 1 0.0197 (7)
Al 0.375 0 0.25 1 0.0171 (5)
O -0.0298(2) 0.0506(2) 0.1493(2) 1 0.0172 (8)
Space group : I a 3 d (cubic) Reliability factors Interatomic distances (Å )
Cell parameters: Rp = 10.02%

Ce-O 2.300(3)
a = 12.01366 (9) Å
Rwp = 13.69% 2.440(3)
b = 12.01366 (9) Å Al-O 1.928(3)
2 = 2.109
c = 12.01366 (9) Å 1.772(2)
Y3Al5O12；Yttrium Aluminum Garnet ( YAG )
Y(X)
X3(A3B2)O12
Al；Tetrahedral(A) Cubic (I a -3 d)
Al；Octahedral(B)
National Taiwan University Citrate Gel
XRD Patterns of (Y2.95Ce0.05)Al5O12 Sintered at Various Temperature for 2 h
1500 ℃
(211)
(420)
(640)
(321)
(422)
(642)
(400)
(521)
(532)
(631)
(721)
(220)
(800)
(440)
(431)
(651)
Intensity
1000 ℃
500 ℃
300 ℃
20 30 40 50 60
2θ
X-ray Absorption and Applications
Synchrotron Radiation and X-ray absorption

X-ray absorption near edge structure; XANES
Extended X-ray Absorption Fine Structure; EXAFS
Applications of X-ray diffraction and absorption
technologies in the secondary batteries and fuel cells
Introduction of National Synchrotron

Radiation Research Center (NSRRC)
同步輻射光之產生
根據電磁學理論，帶電粒子的運動速度或方向改變
時會放射出電磁波。當電子以接近光速飛行，受到
磁場作用而發生偏轉時，因相對論效應使得電子以
接近光速作圓周運動時，所發射之電磁波集中於切
線方向，此即為同步輻射光源。而不像行動電話產
周長: 120 m 生之電磁波像四面八方散去。
周長: 72 m
長度: 72 m
電子束由電子槍產生後，經直線
加速器加速至能量為5千萬電子
伏特，電子束進入周長為72m之
增能環後，繼續增加能量至15億
電子伏特(1.5 GeV)，其速度非常
接近光速(0.99999995倍)。
同步輻射光的科學應用
Materials Chemistry Laboratory 1993年完工啟用; 1994/4開放供國內外使用
Department of Chemistry (全世界第三座第三代同步輻射光源加速器)
TLS (1.5Gev)
(Taiwan Lighting Source)
1986-1993
TPS (3GeV)
National Taiwan University (Taiwan Photo Source)
2007-2015
TLS (1.5Gev)
(Taiwan Lighting Source)
1986-1993
線型加速器： 150MeV, 3Hz

增能環： 496.8m, 10 nm-rad at
3GeV, 3Hz
儲存環： 518.4m, 1.6 nm-rad
3GeV, 24 DBA
GeV: 10億電子伏特 (能量單位)

Materials Chemistry Laboratory 同步加速器聚頻磁鐵光亮度比較
National Taiwan University (TLS, SLS, Diamond, SPring-8, TPS)
SLS: Swiss Light Source (2.4 GeV)
DLS: Diamond Light Source (UK; 3GeV))
Spring-8: Super Photon Ring (Japan 8GeV)
Wavelength (nm)
100 10 1 0.1 0.01
Brilliance (Phot/s/0.1%bw/mm2/mr2)
21 TPS_IU22_5m
10 TPS_EPU48_7m
20 SPring8_IU32
10
TPS 3 GeV
19 other facilities SLS_IU19
10
TLS 1.5 GeV
TLS_EPU56
18
10
17
10 Diamond_IU21
TLS_U90
16
10 TPS_Bending magnet
15
10 TLS_SW60
1 2 3 4 5
10 10 10 10 10
Photon Energy (eV)
台灣大學化學系．材料化學實驗室 2014
2015
台灣光子源
The first synchrotron light from TPS storage

ring at 3 GeV, 1 mA
December 31, 2014
2015
加速器光源的雙環傳奇
台灣光子源成為世界光年的國際焦點
台灣光子源已成為世界光年的國際焦點!
科學
Science
News, 2015/01/30
物理世界
Physics World
News, 2015/03
CERN科學通訊
CERN Courier
4月號封面故事
亞太物理學會聯合會刋
AAPPS
4月號封面故事
自然光子學
Nature Photonics
5月號専文
X光光源亮度演進圖
超亮X光光源能讓先
前看不到的被看到(微
區/動態)，先前量不
到的被量到(微量)
1. 開發新穎材料
2. 綠色能源科技
3. 奈米電子元件
4. 藥物設計研發
5. 探索生命奧妙
6. 生醫顯微技術
7. 癌症診斷治療
8. 永續環境科學
9. 食品安全檢測
10. 藝術司法鑑識
Department of Chemistry 離子與中性原子
光電子
反射光子
螢光
同步加速器光源
表面吸附物
試樣
非彈性散射
缺陷
布拉格繞射穿透光子
勞伊反射
超亮X光神燈「台灣光子源」的科研契機
 利用超亮X光光源，我們可以藉由繞射、散射、反射、吸
收、螢光等多種實驗技術，以及影像和能譜方法，獲得多
重尺度下物質之形貌、原子排列、電子與磁性結構、化學
組態、元素分佈等關鍵訊息。
 超高亮度的TPS，能讓先前看不到的被看到(微區/動態)，
讓先前量不到的被量到(微量)。
 可促使台灣科技界在物質科學(物理、化學、生物)、生醫
科技(藥物、影像、治療)、半導體科技(製程、特性量測)、
能源科技、食品安全、環境科學、地球科學、天文、藝術、
考古及其他各種與材料及奈米科技相關之基礎與應用研究
大放異彩。
環境復育與能源淨化：
先進能源轉換
燃料電池工作示意圖
Catalyst Layers (~10  m)
CO2 H2O
H2O
H+
6e- 6e-
CATHODE
ANODE
CH3OH
Current CH3OH, H2O Current

Air (O2) Collector
Collector
Diffusion Layers (~100 m)
Pt Co
Co(OH)2 PtCoOx PtCoOx+d
Oxidation Oxidation
Pt cluster Pt cluster Pt cluster

Reduction Reduction
Lower Voltage OCP Higher Voltage
台灣大學化學系．材料化學實驗室恐龍胚胎化石中的有機殘留物
Materials Chemistry Laboratory Embryology of Early Jurassic dinosaur from China
Department of Chemistry with evidence of preserved organic remains
National Taiwan University Nature, 496, 210 (2013)
Robert R. Reisz1*, Timothy D. Huang(黃大一)2, Eric Roberts3, ShinRung Peng(NCKU彭信榮)4, Corwin Sullivan5, Koen Stein6, Aaron
LeBlanc1, DarBin Shieh(NCKU 謝達彬)4, RongSeng Chang(NCU 張榮森)7, ChengCheng Chiang(NSRRC 江正誠)8, ChuanWei Yang9,
ShiMing Zong 10
本中心與加拿大多倫多大學生物系Robert R. Reisz 院士合作利用BL14A1紅外光譜顯微實驗站進行

紅外光譜影像掃瞄，同步輻射紅外光譜影像的結果提供遠侏儸紀中國大華龍胚胎腿骨化石中仍有殘
留物的有力證明。此一結果已發表在近期的Nature並獲選為封面故事。
Nature cover story The international team Reconstructed embryonic skeleton of Early Jurassic sauropodomorph
Chuxiong (中國雲南楚雄) Prefectural Museum, no. C2019 2A233
Infrared spectral images of organic remains within embryological fossil section
Thickness ~30 um SR-IMS材料化學-晶體與電子結構

end-station 139/246
TPS之使命與願景
 成為世界頂尖的超高亮度同步加速器光源，建構世界一流的跨領
域實驗設施，取得國際領先地位。
 開創嶄新實驗技術，拓展科學研究領域，特別是生物醫學及奈米
科技，促使我國學術研究更臻世界頂尖水準。
 協助高科技工業進行產品研發與製程優化，提升我國的產業科技
競爭力。
 吸引國際團隊前來進行實驗或建造其專屬光束線，增進國際合作，
提升我國的國際能見度與國際聲望。
 成為延攬國內外傑出人才長期在我國從事跨領域尖端科學研究之
重要誘因。
 引導、培育年輕學子投入尖端科學研究，做出影響深遠的重大科
學發現。
1 ~ 50 µm (FWHM) @ 0.98Å:
1.0x1012 ph/s, with 50 µm x 50 µm Dhn/hn: 10-8
coherent length: 5 ~ 22 mm
E resolving power: 70,000
2.8 m X 1 m
台灣光子源第一期光束線
(7座)
05A、09A、21A、25A、41A
及 45A 將於2015年完工；
23A 將於2016年完工。
100 nm x 100nm
3 mrad x 3 mrad
@ sample ~ 1.7× 1013 ph/sec

4.5 m(H) × 10 m (V) 40 nm at 10 keV
Energy resolution:
coherent flux: ~ 5 x 1010 phs/sec
8 meV @ 530 eV; 20 meV at 900 eV
@ 6 keV, 1x1 m2
Soft X-ray CDI
Dynamics from ms to s
CDI
台灣光子源第二期
光束線 (18座)
12 ID, 6 BM
現埸的朋友們
大家一起來集氣！
讓台灣光子源的光芒
照耀二十一世紀的世界科技舞台！
National Taiwan University Transitions involoved in various spectroscopies
(a) (b) (c) (d)

KE
EF
EB
Photoelectron X-ray absorption X-ray emission Auger electron emission

spectroscopy; PS spectroscopy; XAS spectroscopy; XES spectroscopy; AES
X-ray spectroscopy
(Resonant inelastic X-ray scattering)
Intensity (a.u)
Intensity (a.u) XES XAS
Intensity (a.u)
XAS
Intensity (a.u)
XAS XES XAS

RIXS
515 520 525 530 535 540 515 520 525 530 535 540 515 520 525 530 535 540 515 520 525 530 535 540
Energy (eV) Energy (eV) Energy (eV) Energy (eV)
National Taiwan University X-ray Spectroscopy
X-ray Absorption Spectroscopy

(XAS)
X-ray Absorption Spectroscopy (XAS)

X光吸收光譜
X-ray Absorption Near Edge Structure (XANES)
X光吸收近邊緣結構
Extended X-ray Absorption Fine Structure (EXAFS)
延伸X光吸收細微結構
自從1895年德國物理學家倫琴（Wilhelm
Conrad Roentgen）發現X光以來，因其波長
介於10-2 Å ～102 Å 之間，接近於原子之大小，
故一直是研究物質原子結構的重要工具。
X光吸收光譜（X-ray Absorption Spectroscopy，XAS），主

要是依據物質對X光的吸收係數μ與該物質的總截面（total cross
section）成正比之關係，來推知物質之原子結構及電子能態等
方面之資料。
K-edge & L-edge

X光吸收光譜主要有兩大應用：一為X光吸收近邊緣結構（X-ray Absorption
Near Edge Structure，XANES），係量測吸收原子的電子性質，例如吸收原子
的電荷密度、電子結構、氧化價數及過渡金屬的d-軌域電子占有率，以及吸
收原子所處在之晶位的對稱性。
1s3d 1s4p
分別以Cr(NO3)3及K2Cr2O7配製1000 ppm Cr+3

及Cr+6水溶液在Cr K-edge (1s4p)之X光吸收
近邊緣
結構。
Pre-edge Absorption
Ti: 1s3d
Ti: 1s4p
K-edge (1s4p) Absorption

EXAFS & XANES
另一為延伸X光吸收細微結構（Extended X-ray Absorption Fine Structure，
EXAFS），則可測得吸收原子周圍之局部（＜10Å ）幾何結構，例如某一配位層
內原子的種類、配位數、吸收原子與周圍原子間的距離，以及排列之雜亂度等之
短程有序結構（short-range order）之參數。

LiCoO2粉末樣品在室溫下的Co K-邊緣
(edge)處之X光吸收圖譜。
當中心原子A的內層電子因吸收X光而被游離時，此種光電子將帶著E-E0的動
能遠離原子核，形成一向外行進的光電子波，其波長為：
h h
e  
p 2m( E-E0 )12
當吸收原子周圍有其他原子B存在時，會將向外行進的光電子波予以背向散射，
假設A、B兩原子相距R，則向外行進與背向散射的光電子波之間存在2R的路
程差，此一路程差將使得二者的相位差為：
1
 2R   8π m( E  E 0) 
2 2
 
2    2 R    2kR
λ
 e   h 2

其中k稱為光電子波向量，常以Å -1其單位。
k  0.2625 ( E  E 0)
1
當電子動能的單位為eV時，則 2
如此，向外行進與背向散射的光電子波間的相位差將隨原子間距離或入射能量而變
化，且產生建設性（同相）或破壞性（反相）干涉，造成在吸收係數上之調諧作用
（modulation），亦即EXAFS振盪。
測量方式一
穿透模式—入射光與偵測器呈180度 (直線)
適用於高濃度或低穿透率樣品
It = I0e-μx（μ = 吸收係數， x = 樣品厚度）
ln (I0/It) = μx
測量方式二
螢光模式
—入射光與偵測器呈90度 (垂直)
適用於低濃度或高穿透率樣品
If 或 Ie 正比於吸收係數
基於詳細的理論推導，EXAFS函數與物質結構參數間的關係如下：
 (k )   kR S (k )F (k )e
Nj
2 j j
 2j k 2  2 R j λ ( k )
e 
sin 2kR j  δ ij (k ) 
j j
Rj：第j層原子與中心原子間之平均距離；
Nj ：第j層中含有的原子個數或稱配位數；
Sj（k）：振幅減低因子，用以反映吸收程序中的多重激發效應；
σj2：Debye-Waller因子，用以瞄述原子排列的雜亂程度，為該
層所有個別原子與中心原子間之距離減去平均距離之平方和；
 (k )   kR S (k )F (k )e
Nj
2 j j
 2j k 2  2 R j λ ( k )
e 
sin 2kR j  δ ij (k ) 
j j
λ（k）：電子的平均自由徑，用以考慮電子的非彈性散射以及
內層電洞半衰期效應；
δij（k）：因中心原子i和背向散射原子j之電位而致的相位偏移；
Fj（k）：原子j對光電子波背向散射的振幅函數；
Σ：表示EXAFS包含了中心原子周圍不同距離之各原子層的貢獻。
j
自原始吸收曲線將平滑背景扣除而分離出EXAFS振盪，
1 再除上圖譜在吸收邊緣處之躍升梯度以進行正規化處理
可得EXAFS函數，亦即χ數據。
為彌補EXAFS振幅隨能量增加而急速衰減，
2 經常將χ乘以kn加權因子。
3
對加權後的EXAFS函數進行傅立葉轉換（Fourier
transformation，FT），則可得如圖之結果。在圖
中各尖峰代表各單一配位層的貢獻，且依距中心
原子遠近不同順序排開。此圖亦稱為準半徑分布
函數（pseudo-radial distribution function）。
Applications of XRD and XAS technologies

in the secondary batteries and fuel cells
Improvement of Performance of
LiMn2O4 Cathode Material via
Chemical Substitution
Secondary Lithium Batteries

Oxygen Transition metal
ions (Co, Ni, Mn) graphite
Lithium
ions
LiMn2O4 I 41/amd (141), tetragonal

a = 5.7667(2) Å , c = 8.6678(4) Å
Jahn-Teller distortion
Distortion of Crystal Structure
dx2-y2
Mn3+ d4 eg dxy
t2g dz2
dxz, dyz
Self redox reaction

Mn3+ Mn2+ ＋ Mn4+
Goals
LixMn2O4 LixCo0.16Mn1.84O4
Original Capacity 125Ah/kg 120Ah/kg
10 cycles 100Ah/kg (20%) 108Ah/kg (10%)
100 cycles 80Ah/kg (36%) 105Ah/kg (12.5%)

J Electrochem. Soc. 1996, 143,
178.
Study the stability effect by the dopant of Co
Li(Mn2-xCox )O4
[ Li(Mn3+1-x Mn4+1Co3+x )O4 ]
Experimental
Li2CO3, MnO2 and Co3O4 XRD
EDS
Li(Mn2-xCox )O4 ( x = 0 ~ 0.5 )
SEM BET
HRTEM
Sintered at 800℃ for 24 hrs in air,then cooled
down to r.t. at a rate of 5℃/min (3 times) Titration
XANES
XRD:- Phase purity Cell

- Crystal structure (Step scan, 0.02o, 10 sec)
[refinement program; GSAS (General structure analysis system)]
Li(Mn2-xCox )O4
Mn3+ 0.645 Å
XRD Refinement Co3+ 0.545 Å
(CN = 6)
Cell volume
8.24 V 560
linear fit of V x = 0.5
(Å )
8.22
555
8.20
x = 0.4
(Å 3)
Cell parameter
550
Intensity
8.18 x = 0.3
a 545
linear fit of a
8.16 x = 0.2
540
0.0 0.1 0.2 0.3 0.4 0.5
x
x = 0.1
(311)
(400)
(111)
x=0
(331)
(511)
(222)
Cubic Fd3m
15 20 25 30 35 40 45 50 55 60
2
Particle Size Li(Mn2-xCox )O4 ( x = 0 ~ 0.5)
x=0 x = 0.1 x = 0.2
x = 0.3 x = 0.4 x = 0.5 1.50 m
National Taiwan University Li(Mn2-xCox )O4
EDS and Surface Area
2.6
EDS BET
100 30
2.4
95 25
2.2
Surface area (m /g)

2
90 20 2.0
Mn
M n ratio %
Co ratio %
85 15 1.8
80 10 1.6
1.4
75 Co 5
1.2
70 0
0.0 0.1 0.2 0.3 0.4 0.5
0.0 0.1 0.2 0.3 0.4 0.5 x
x 材料化學-晶體與電子結構 178/246
台灣大學化學系．材料化學實驗室 NSRRC
Department of Chemistry X-ray absorption near edge structure
(XANES)
Li(Mn2-xCox)O4 ( x = 0 ~ 0.5)
0.0
XANES EXAFS 2 p 3/2 3 d Mn-2p edge
-0.5 2 p 1/2 3 d
Cu
-1.0
M nO 2
Absorption
constructive x = 0.5
-1.5
Relativity Abs.
-2.0 x = 0.4
Cu
-2.5
x = 0.3
destructive
x = 0.2
-3.0
8800 9000 9200 9400 9600 9800 10000 10200
Energy (eV) x = 0.1
x=0
M n 2O 3
635 640 645 650 655 660

Energy (eV)
Materials Chemistry Laboratory NSRRC
X-ray Absorption Near Edge Structure (XANES)
Li(Mn2-xCox )O4
Co-2 p edge
x = 0.5
x = 0.4
x = 0.3
x = 0.2
x = 0.1
Co 3 O 4
Co 2 O 3
CoO
770 775 780 785 790 795 800 805

Energy (eV)
Materials Chemistry Laboratory Co3+ 3d6
Co K-edge spectra for Li(Mn2-xCox)O4
B : Co 1s2.0
3d7L 4p0 Co 1s 3d7L 4p1 Co 3d7L
1.8 Li(M n 2-x Co x )O 4 (x = 0.1)
1.6
LiM n 1.84 (Co 0.16-y Ni y )O 4 (y = 0.04)
1.4 △
Co 2 O 3
1.2
ln (I 0/I t)
1.0 CoO 0
0.8 Co 3d6
0.6
Co Co
0.4 B Co3+ GS
CoO
0.2 Co O 2 3
0.0 Li(M n Co )O (x = 0.1)2-x x 4
-0.2 A LiM n (Co N i )O (y = 0.04)

1.84 0.16-y y 4
-0.4
7690 7700 7710 7720 7730 7740 7750 7760 7770
Energy (eV)
A : Co 1s Co 3d t2g6 eg0 + O 2p
ref: M. G. Kim et al., J. Phys. Chem. B 103, 6457 (1999).
Department of Chemistry Mn3+ : 0.645 Å
National Taiwan University Co3+ : 0.61 Å
Li(Mn2-xCox)O4 K-edge EXAFS Mn4+ : 0.530 Å
(CN = 6)
Co-O C o 16d -Co/M n 16d
Mn K-edge Co K-edge x = 0.5

x = 0.5
x = 0.4
x = 0.4
F(R)
F (R)
x = 0.3
x = 0.3
x = 0.2
x = 0.2
x = 0.1 x = 0.1
x=0 0 1 2 3 4
0 1 2 3 4 R (Å )
R (Å )
0.074
1.98 M n-O Li(M n Co )O Mn-O
Mn environment 2-x x 4 2.92
(Å )
(Å )
Co-O 0.073
1.96 2.91
6 Mn-O 1.914(26) Å , 0.0720.074 Å (x = 0)

Mn-M
 2.90 Co-M
(Å )
Bond distance
1.94
Co environment
Bond diatance
2.89
1.92 0.071
6 Mn-O 1.911(30) Å ,  0.068 Å (x = 0.5) • 6 Co-O 1.919(43) Å (x = 0.1)



2.88
1.90 0.070
2.87
1.88
Jahn-Teller Mn3+ • 6 Co-O 1.932(29) Å (x = 0.5)
0.069 2.86
2.85
1.86 0.068
 Oh Co3+
0.0 0.1 0.2 0.3 0.4 0.5
0.0 0.1 6 Mn-M 2.915(1) Å ,  0.076 Å (x = 0)

0.2 0.3 0.4 0.5 0.0 0.1 0.2
x
0.3 0.4 0.5
x
• 6 Co-M 2.863(46) Å
x
 6 Mn-M 2.885(1) Å ,  0.074 Å (x = 0.5)
Materials Chemistry Laboratory NSRRC
Synchrotron ( = 1.3271 Å ) powder diffraction spectra

(111)
Conventional
 = 1.3271 Å
K 
(400)
( C u
(311) radiation,  =
(440)
(531)
x = 0.1
(511)
(333)
(444)
(622)
(533)
(331)
(222) 1.5406 Å ) and
synchrotron ( =
x=0 1 . 3 2 7 1 Å )
powder XRD
spectra of the
 = 1.5406 Å
(333)
(440)
(311)
(111)
(400)
(531)
(511)
(222)
x = 0.1 (331) LiMn2-xCoxO4

with x = 0 and
0.1 at room
x=0
temperature.
10 20 30 40 50 60 70
2
LiMn2O4 NSRRC
Temperature dependence of the relative area of the

(400) peak indexed by the space group Fd3m (cubic)
G rease Be and the (004) peak indexed by Fddd phase
(orthorhombic) for the LiMn2O4 sample.
0.35 0.35
25 K cooling
0.30 0.30
Area[ Fd 3 m ,(400)]/Area[ Fd 3 m ,(111)]
0.25 0.25
100 K
Relative Area
Relative Area
0.20 0.20
Relative Intensity
210 K 0.15 0.15
0.10 0.10
220 K
0.05 0.05
Area[ Fddd ,(004)]/Area[ Fd 3 m ,(111)]
0.00 0.00
270 K
0 30 60 90 120 150 180 210 240 270 300 330
Tem perature (K )
290 K
(111)
Powder X-ray diffraction patterns of

(311)
(222)
(400)
300 K
(331)
LiMn2O4, taken between 300 and 25 K with

(333)
(511)
(440)
(531)
synchrotron of wavelength 1.3271 Å . Small

diffraction peaks are marked by grease and
10 20 30 40 50 60 Be sample holder.
Tem perature (K )
LiMn2O4
Fd3m Fddd
Table
Comparison of calculated and observed peak positions for the space
group Fd3m and Fddd of LiMn2 O4 with synchrotron of wavelength
(333)
(511)
(440)
(531)
1.3271 ?
LiM n 2 O 4 Fd 3m Fddd
300 K o o a
(hkl) 2cal( ) 2obs( ) (hkl) 2cal(o )b 2obs(o )c
290 K (111) 16.03 16.04 (111) 16.03 16.04
285 K (311) 30.97 31.00 (311) 30.87 31.00
280 K (131) 30.97 31.00
270 K (113) 31.10 31.00
Fd3m (222) 32.39 32.41 (222) 32.39 32.41
260 K
250 K (400) 37.57 37.61 (400) 37.39 37.61
240 K (040) 37.56 37.61
(004) 37.78 37.77
(151)
230 K
(333)
(331) 41.09 41.14 (331) 41.00 41.14

(440)
(404)
220 K
(313) 41.10 41.14
210 K (133) 41.18 41.14
Fddd 200 K (333) 49.46 49.51 (151) 49.45 49.51
180 K (511) 49.46 49.51 (333) 49.47 49.68
150 K (440) 54.18 54.23 (440) 54.04 54.02
125 K (404) 54.21 54.23
100 K (531) 56.89 56.96 (531) 56.69 56.96
75 K (513) 56.77 56.96
50 K (351) 56.81 56.96
25 K (153) 56.95 56.96
a 300 K, b ref: K. Oikawa, Solid State Ionics, 1998, 109, 35. c 200 K
46 48 50 52 54 56 58
2
LiM n 2 O 4
Intensity ( arbitrary unit )
Neutron Scattering
15'-20'-7'
10 K
35 K
90 K
150 K
200 K
250 K
300 K
0 20 40 60 80 100 120 140 160

Scattering angle 2 
Materials Chemistry Laboratory Mn3+ Mn4+
National Taiwan University LiMn2O4
HRTEM
(a) (b) (c)
(400)
a*
b*
(040)
T = 230 K
高解析電子顯微鏡所探討之LiMn2O4材料，沿晶體[001]方向觀察LiMn2O4材料之
(a)電子繞射 (b)原子影像 (c) LiMn2O4存在於低溫之電子繞射圖
ref: J. Rodriguez-Carvajal et al., Phy. Rev. Lett. 81, 4660 (1998).
Materials Chemistry Laboratory Mn3+ Mn4+
Orthorhombic Fddd
Mn3+ Mn4O4 cube

Mn4+
Li+
a ref: J. Rodriguez-Carvajal et al., Phy. Rev. Lett. 81, 4660 (1998).

台灣大學化學系．材料化學實驗室 Cooling
National Taiwan University LiMn1.9Co0.1O4
(511)
(440)
(333)
LiM n 1.9 Co 0.1 O 4
(531)
310 K
300 K MnO6
295 K
290 K
285 K Li
280 K
275 K
265 K
255 K
240 K
220 K
The synchrotron diffraction
210 K
patterns of LiMn1.9Co0.1O4
205 K
sample showing the cubic
200 K
180 K spinel peaks (333), (511), (440),
150 K and (531) in the 2q range of 46
125 K - 59o from 300 K down to 25 K.
100 K
As can be seen, there is no
75 K
50 K
peak split or broadening from
25 K room temperature to low
temperature.
46 48 50 52 54 56 58
2
National Taiwan University AHB553048 Discharge Characteristics Chart
4.4
充電: 先定電流(cc; 350 mA)充至4.2V(使鋰離子至負極表面)， 0.2C
4.2 0.5C
再定電壓使電流降至定電流值之5%而停止(使鋰離子至負極裡面) 1.0C
4 2.0C
3.8
Voltage(V)
3.6
3.4
3.2 Cha rge : 0. 5C(350mA) t o 4. 2V,

5% Cha rge Curre nt c ut -off
3 Di sc ha rge : 0. 2C/ 0. 5C/ 1. 0C/ 2. 0C t o 3. 0V
2.8
0 100 200 300 400 500 600 700
Capacity(mAh)
•Capacity(電容量)是被設計出來的，單位為mAh
•C rate指的是充電或放電之電流量大小，單位為mA (or A)，
通常定義1C rate即為在1小時內放電須達到設計之容量，
•如電池電容量為700mAh，其1C即為700mA (1小時內放電須達到設計之容量)，
•而0.5C為350mA (2小時內放電須達到設計之容量)
，0.2C為140mA (5小時內放電須達到設計之容量) ，2C則為1400mA (0.5小時內放電須達到設計之容量)
4.4
4.2
4.0
3.8
Voltage (V)
3.6 co0
co01 x=0
3.4
co02
3.2 co03 x = 0.4
3.0 co04
co05 x = 0.5
2.8
x = 0.3 x = 0.2 x = 0.1
2.6
0 10 20 30 40 50 60 70 80 90 100 110 120 130
Capacity (m Ah/g)
Li(Mn2-xCox)O4 (x = 0 ~ 0.5) 於c/5電流下之電壓與放電電容量關係圖
Li(Mn2-xCox)O4（x = 0 ~ 0.5）
130
x=0
120 x = 0.1
x = 0.2
110
Capacity (mAh/g)
100
90
80 x = 0.3 x = 0.4
x = 0.5
70
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Cycle Number
新負極材料之發展
- LiVMoO6
LiVMoO6
powder XRD
Wet-chemical Synthesis
Method
400℃
540℃
600℃
Fig. 3. X-ray diffraction patterns of combustion-derived materials

(precursor) calcined at various temperatures for 1 h in air: (a) 400°C,
(b) 540°C and (c)600°C.
Ref.: M.S. Michael et al. Int. J. Inorg. Mater. 2, 261 (2000).
Department of Chemistry -Theoretical capacity: 107 mAh/g
-Experimental capacity: 92 mAh/g
charge
discharge
x in LixVMoO6
Fig. 6. First charge and discharge characteristics of a Li||LiVMoO6 non-aqueous

cell employing 1M LiBF4(EC+DMC); the product calcined at 540°C at a current
density of 0.20 mA/cm2.
Ref.: M.S. Michael et al. Int. J. Inorg. Mater. 2, 261 (2000).

Questions of Michael’s work [Int. J. Inorg. Mater. 2, 261 (2000)] ?
• XRD pattern not indexed
• Only one cycle of the cell test

• LiVMoO6 (V5+ → V6+? or Mo6+ → Mo7+?)
Motivation of our study……
Synthesis of LiVMoO6
XRD
Li2CO3 ＋ V2O5 ＋ MoO3
(Li:V:Mo＝1:1:1)
SEM EDS
HRTEM
Sintered at 550℃ for 24 hrs in air, then
cooled down to r.t. at a rate of 5℃/min
XANES
Final products Cell test
XRD - Phase purity in-situ XRD

- Crystal structure (Step scan, 0.02o, 10 sec)
[refinement program; GSAS (General structure analysis system)]
XRD refinement
1.0
0.8
0.6
4
Counts × 10
0.4
0.2
0.0
-0.2
-0.4
10 20 30 40 50 60 70 80 90 100 110
2
National Taiwan University XRD refinement
Monoclinic cell
atoms x y z fraction Ui/Ue×100
Li 0.00000 0.00000 0.00000 1 5.4(17)

V 0.18577(15) 0.00000 0.65371(21) 0.5 2.52(6)
Mo 0.18577(15) 0.00000 0.65371(21) 0.5 2.52(6)
O 0.9676(7) 0.00000 0.2783(8) 1 3.85(26)
O 0.3329(7) 0.00000 0.8957(9) 1 4.20(26)
O 0.3124(7) 0.00000 0.4309(9) 1 5.24(30)
space group: C12/m1 reliability factor bond distances (Å )
lattice parameters: Rp = 7.25 % V(Mo)-O 1.6839

a = 9.3443(4) Å Rwp = 10.69 % 1.7180
b = 3.64610(14) Å χ2 = 2.11 2.1833
c = 6.63636(25) Å 1.8894
Crystal structure
LiVMoO6
SEM LiVMoO6
β= 111°28´
b
c
7.5 m 15 m
HRTEM
c*
a* b*
Li c
V, Mo b
1 nm
X-ray absorption near edge structure
LiVMoO V K-edge
(XANES)
6
Normalized absorption 1.5
1.0
1s→3d
V 2O 3
VO 2
0.5
V 6 O 13 (V: 4.3+)
V 2O 5
LiVM oO 5
LiVM oO 6
0.0
5460 5465 5470 5475 5480 5485 5490 5495 5500
Energy (eV)
X-ray absorption near edge structure
(XANES)
LiVMoO6 Mo K-edge
M oO 2
1.0 M o foil
Normalized absorption
M oO 3
LiVM oO 6
LiVM oO 5
0.6
Mo(0)
0.5 0.5
Mo(4+)
0.4 Mo(6+)
0.3
20000 20005 20010 20015
0.0
19960 19980 20000 20020 20040 20060 20080 20100
Energy (eV)
EXAFS fitting
National Taiwan University 7
1.5
1.718
white line V K-edge
Norm alized absorption
FT magnititude
1.0 5
1s→3d
1s→4p 4
2.209
0.5 5480 2.546
3
3.160
2
0.0
1
differentiated data
-0.5
0
5450 5475 5500 5525 5550 5575 0 1 2 3 4 5 6 7 8 9 10
Energy (eV) R (angstrom )
6
3
kχ
4 kχ
LiVMoO6
3
EXAFS ．k
2 2
kχ
-2
-4
0 5 10 15 20
-1
k (angstrom )
National Taiwan University Coin-cell test: Cathode
4.2
charge
4.0
Potential (V vs. Li /Li)
3.8
+
3.6
3.4
discharge
3.2
3.0
2.8 cycle number increasing
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14

Charge-discharge capacity (m Ah/g)
National Taiwan University Coin-cell test: Anode
18v1-1
3.0 18v2-1
18v3-1
18v6-1
2.5
Potential (V vs. Li /Li)
3-0.01 V
+
2.0
1.5
1.0
0.5
0.0
0 200 400 600 800 1000 1200
Capacity (m Ah/g)
硬幣型電池組裝示意圖
電池蓋 kapton
彈簧墊
鎳片
鋰金屬
O型環

電解液 
隔離膜

電解液 
電池極板
電池蓋
In-situ experiments
Reference electrode (SCE)
Cathode
Working electrode
I sample Au
I0
Pt Synchrotron
radiation
Kapton
Counter electrode
9M LiNO3 (aq)
coin-cell
synchrotron radiation
λ = 1.326 Å
_ +
In-situ XRD
20 30 40 50 60 70 80
2
coin-cell
synchrotron radiation
λ = 1.326 Å
In-situ XRD
Discharge
3.0
/Li)
A 2.5 A
+
2.0
Potential (V vs. Li
B 1.5
1.0 B
DE
C 0.5
F
GI
Normalized intensity
C H
0.0
D 0 500 1000 1500 2000 2500
C apacity (m A h/g)
E
1.0
F 0.8
4
Counts × 10
0.6
G
0.4
H 0.2
0.0
I
10 20 30 40 50 60
10 15 20 25 30 35 40 45 50 2 theta (CuK )
2 theta (λ = 1.326 Å )
In-situ XRD
Discharge
3.0
/Li)
J
2.5
+
2.0
Potential (V vs. Li
K 1.5
1.0
L 0.5
J K L MN O P
Q
0.0
0 500 1000 1500 2000 2500
M Capacity (m Ah/g)
1.0
N
0.8
4
O
Counts × 10
0.6
0.4
P 0.2
0.0
Q
10 20 30 40 50 60
10 15 20 25 30 35 40 45 50 2 theta (CuK )
2 theta (λ = 1.326 Å )
In-situ XRD
Charge
3.5
/Li)
R 3.0
+
2.5
Potential (V vs. Li
S 2.0
ZΛ
1.5 Y
T X
1.0 W
T U V
RS
0.5
U
0 100 200 300 400
C apacity (m A h/g)
V
W 1.0
0.8
X
4
Counts × 10
0.6
Y 0.4
Z 0.2
0.0
Λ
10 20 30 40 50 60
10 15 20 25 30 35 40 45 50 2 theta (CuK )
2 theta (λ = 1.326 Å)
SEM-EDS
before discharge
State Element Atomic %

before charge V 58.18
Mo 41.82
after discharge V 57.32
Mo 42.68
after discharge
Coin-cell test
4
MnO 2
LiMn 2 O 4
Cell potential (V)
3
Charge Discharge
LiVMoO 6
2
Li 1+x VMoO 6 +unknown

0
0 200 400 600 800 1000 1200
Charge-discharge capacity (mAh/g)
Summary (LiVMoO6)
LiVMoO6 was successfully synthesized using the conventional solid state reaction
method, and its chemical and physical properties were examined by several
analytic methods.
We have proven that LiVMoO6 does not possess good structural characteristics for
a lithium half cell (Li / LiVMoO6) as a cathode in non-aqueous electrolyte
environment.
LiVMoO6 might be considered as a new anode material of choice for developing a

Li-ion rechargeable battery technology. (The cells exhibit three stable discharge
plateaus and deliver capacities of over 1200 mAh/g during the first discharge.)
燃料電池之作用原理
負極(anode)
H2 → 2H+ + 2e¯
電解質
polymer
正極(cathode)
1/2 O2 + 2H+ + 2e¯ → H2O
Materials Chemistry Laboratory Ref.: T. Schultz et al., Chem. Eng. Technol. 24, 12 (2001).
Direct Methanol Fuel Cell (DMFC)
Anode Cathode
National Taiwan University 甲醇催化氧化反應
– H+ – H+ – H+ – H+
Pt之CO毒化作用
– e– – e– – e– – e–
PtRu雙金屬觸媒作用機制
Ref.: T. Schultz et al., Chem. Eng. Technol.

24, 1223 (2001).
直接甲醇燃料電池負極觸媒材料
PtM/C (M = Ru and/or Mo) catalysts
The Phases of the Nanoparticles formed on the

PtRu Bimetallic Catalysts
(1) H2PtCl6 + RuCl3 + C

reduction PtRu alloy/C
(2) Pt/C + RuCl3 or
Pt/C +Ru/C
(3) Ru/C + H2PtCl6
reduction Pt1-xRux alloy/C
(1-x)H2PtCl6 + xRuCl3 +C or
(1-x)Pt/C + xRu/C
Pt (fcc) ? Ru (hcp)
Materials Chemistry Laboratory Ref.: J. M. Hutchnson, Jr., Platinum Met. Rev. 16, 88 (1927).
Phase Diagram of Bulk Pt-Ru
2200 Liquid
Temperature (° C)
1800
hcp
two-
fcc phase
1400
region
1200
0 20 40 60 80 100
Pt Atomic Percent of Ru Ru
 How about nanoscaled Pt-Ru?
Fcc (Pt) vs hcp (Ru)

Oct. 2, 2002
Platinum (Pt) (111)

JCPDS: 87-0647
Sys.: Cubic fcc
Relative intensity (a.u.)

S.G.: Fm-3m (225)
a = 3.878 A° (200)
(220)
Ruthenium (Ru) (101)

JCPDS: 06-0663
Sys.: Hexagonal hcp
S.G.: P63/mmc (194)
°
a = 2.7058 A, (100)
c = 4.2819 A° (002)
(102) (110) (103)
10 20 30 40 50 60 70 80
2  (degree)  :Pt & Ru standard.opj
BL17A1 (XRD)
XRD Oct. 18, 2002
Pt-Ru (111)
(a) H2PtCl6 + RuCl3 + C

Pt-Ru (200)
(a) C (002) Pt-Ru (220)
(b) Pt/C + RuCl3
Ru (002) (c) Ru/C + H2PtCl6
Ru (100)
Ru (101) Ru (103)
Ru (102) Ru (110)
(b)
Impregnation condition:
Starting materials were
(c) reduced under H2 flow
at 250°C for 4 hours.
10 20 30 40 50 60 70 80
2  (degree)
:CSIST-XRD-021018.opj
PtRu/C系列
XRD (at NSRRC)
Mar. 28, 2003
(111) Pt-Ru/XC-72
(a) 30 % Pt/C (100:0 a/o)
(200)
(220)
(a) (b) 29 % Pt-1 % Ru/C (95:5)
fcc
C (002)
(b)
(c) 28 % Pt-2 % Ru/C (90:10)
(d) 25 % Pt-5 % Ru/C (80:20)
(c)
(e) 20 % Pt-10 % Ru/C (55:45)

(d)
(f) 15 % Pt-15 % Ru/C (35:65)
fcc + hcp
R uO 2
(e)
(002)
(101)
Ru (100) Ru (110)
(f)
10 20 30 40 50 60 70 80 90 100110120
2  (degree)
 = 1.32721 A
(a) 30 % Pt/C (100:0 a/o)

(b) 29 % Pt-1 % Ru/C (95:5)
(c) 28 % Pt-2 % Ru/C (90:10)
TEM
100 nm
100 nm
30% Pt/C (100:0)

20 nm
TEM
20 nm
20% Pt-10% Ru/C (45:55)
20 nm
HRTEM
28% Pt-2% Ru/C (90:10) lattice image
fringe
2 nm
5 nm
(111) plane of Pt-Ru alloy 25% Pt-5% Ru/C (80:20)
HRTEM
twined particle
20% Pt-10% Ru/C (45:55) 15% Pt-15% Ru/C (35:65)

Intrinsic stacking fault
XANES
Apr. 9, 2003
Normalized absorption [ln(I 0/I t)]
Pt L- III-edge
1.0
0.5 30 % Pt/C (100:0 a/o)

28 % Pt-2 % Ru/C (90:10)
25 % Pt-5 % Ru/C (80:20)
20 % Pt-10 % Ru/C (55:45)
15 % Pt-15 % Ru/C (35:65)
Pt foil
0.0
11540 11560 11580 11600 11620 11640
Energy (eV)
Pt LIII-edge XANES  :diff-PtRu-ratio-L3(SP8).opj
XANES Apr. 9, 2003

Pt L- III-edge
30 % Pt/C (100:0 a/o)

28 % Pt-2 % Ru/C (90:10)
25 % Pt-5 % Ru/C (80:20)
20 % Pt-10 % Ru/C (55:45)
15 % Pt-15 % Ru/C (35:65)
Pt foil
11560 11565 11570

Energy (eV)
 :diff-PtRu-ratio-L3-wl(SP8).opj
Pt LIII-edge XANES (contd.)
XANES Apr. 9, 2003

Pt L- II-edge
1.0
0.5
30 % Pt/C (100:0 a/o)

28 % Pt-2 % Ru/C (90:10)
25 % Pt-5 % Ru/C (80:20)
20 % Pt-10 % Ru/C (55:45)
15 % Pt-15 % Ru/C (35:65)
Pt foil
0.0
13250 13275 13300 13325 13350 13375

Energy (eV)
 :diff-PtRu-ratio-L2(SP8).opj
Pt LII-edge XANES
XANES Apr. 9, 2003
Normalized absorption [ln(I 0/I t)] Pt L- II -edge

1.0
0.5
30 % Pt/C (100:0 a/o)
28 % Pt-2 % Ru/C (90:10)
25 % Pt-5 % Ru/C (80:20)
20 % Pt-10 % Ru/C (55:45)
15 % Pt-15 % Ru/C (35:65)
Pt foil
0.0
13260 13270 13280 13290
Energy (eV)
Pt LII-edge XANES (contd.)  :diff-PtRu-ratio-L2-wl(SP8).opj
台灣大學化學系．材料化學實驗室 Apr. 17, 2003
0.345
0.340
d-band unoccupied states

0.335
per Pt atom
1.6 0.330
Normalized absorption coefficient
1.4
0.325
1.2
1.0 0.320
L III-edge
0.8
0.315
0.6 L II-edge
0.4 0.310
0 10 20 30 40 50 60 70
0.2 Atom ic percentages of Ru in Pt+Ru (% )
0.0  :diff-PtRu-ratio-hT.opj
AS (empty)
-40 -20 0 20 40 60
Energy (eV)
Fermi level
DE
5d5/2 AS (filled) (5d5/2 – 5d3/2)
5d3/2
2p3/2
LIII
材料化學-晶體與電子結構 LII 2p1/2 236/246
XANES Apr. 15, 2003
Ru K-edge
Normalized absorption [ln(I0/It)]
1.0
0.5
28 % Pt-2 % Ru/C (90:10)
25 % Pt-5 % Ru/C (80:20)
20 % Pt-10 % Ru/C (55:45)
15 % Pt-15 % Ru/C (35:65)
Ru powder
RuO2
0.0
22050 22100 22150 22200 22250 22300 22350
Energy (eV)
 :diff-PtRu-ratio-K(SP8).opj
XANES
Apr. 15, 2003
Normalized absorption [ln(I 0/I t)] Ru K -edge
1.0
0.5
28 % Pt-2 % Ru/C (90:10)
25 % Pt-5 % Ru/C (80:20)
20 % Pt-10 % Ru/C (55:45)
15 % Pt-15 % Ru/C (35:65)
Ru powder
RuO 2
0.0
22100 22120 22140 22160 22180
Energy (eV)
 :diff-PtRu-ratio-K-wl(SP8).opj
EXAFS
15 35
30% Pt/C Pt-Pt 30% Pt/C (100:0)
28% Pt-2% Ru/C 2.792 28% Pt-2% R u/C (90:10)
25% Pt-5% Ru/C 30 25% Pt-5% R u/C (80:20)
10 20% Pt-10% Ru/C 20% Pt-10% R u/C (55:45)
15% Pt-15% Ru/C 15% Pt-15% R u/C (35:65)
25
FT magnititude
5
20
k 
0 15
3
Pt-Ru
10 2.438
-5
5 Pt-O
-10 0
5 10 15 0 1 2 3 4 5 6 7
k R (angstrom )
k-weighted χdata
XRD (at NSRRC) May 29, 2003

PtMo/C系列
(111)
(200)
(220) (a) 30 % Pt/C (100:0 a/o)
C (002) (a)
(b) 29 % Pt-1 % Mo/C (95:5)
fcc
(b) (c) 28 % Pt-2 % Mo/C (90:10)
(d) 25 % Pt-5 % Mo/C (75:25)
(c)
(e) 20 % Pt-10 % Mo/C (50:50)
(d) (f) 15 % Pt-15 % Mo/C (30:70)
fcc + bcc
(e)
(f)
10 20 30 40 50 60 70 80 90 100110120
2  (degree)
(a) 30 % Pt/C (100:0 a/o)

(b) 29 % Pt-1 % Mo/C (95:5)
(c) 28 % Pt-2 % Mo/C (90:10) 材料化學-晶體與電子結構 240/246
XANES
Apr. 9, 2003
Pt L- III-edge
1.0
0.5 30 % Pt/C (100:0 a/o)

28 % Pt-2 % M o/C (90:10)
25 % Pt-5 % M o/C (75:25)
20 % Pt-10 % M o/C (50:50)
15 % Pt-15 % M o/C (30:70)
Pt foil
0.0
11540 11560 11580 11600 11620 11640
Energy (eV)
 :diff-PtM o-ratio-L3(SP8).opj
Pt LIII-edge XANES
XANES Apr. 9, 2003

Pt L- II-edge
1.0
0.5
30 % Pt/C (100:0 a/o)

28 % Pt-2 % M o/C (90:10)
25 % Pt-5 % M o/C (75:25)
20 % Pt-10 % M o/C (50:50)
15 % Pt-15 % M o/C (30:70)
Pt foil
0.0
13250 13275 13300 13325 13350 13375

Energy (eV)
 :diff-PtM o-ratio-L2(SP8).opj
Pt LII-edge XANES
Electronic effect Apr. 17, 2003

hT (d-band unoccupied states per Pt atom)
0.345
PtRu/C
0.340
0.335
PtMo/C
0.330
0.325
0.320
0.315
0.310
0 10 20 30 40 50 60 70
Atomic percentages of M (= Ru or Mo) in (Pt+M) (%)
:diff-PtRu-ratio-hT.opj
XANES
Apr. 15, 2003
Mo K -edge
1.0
28 % Pt-2 % M o/C (90:10)

0.5 25 % Pt-5 % M o/C (75:25)
20 % Pt-10 % M o/C (50:50)
15 % Pt-15 % M o/C (30:70)
M o powder
M oO 2
M oO 3
0.0
19990 20000 20010 20020 20030 20040
Energy (eV)
 :diff-PtRu-ratio-K(SP8).opj
Mo K-edge XANES
Summary
• The carbon supported Pt-M (M=Ru and Mo) bimetallic catalysts
with single alloy phase can be synthesized by one-step reduction
process.
• The relationship between the compositions and the phases of
the nanosized bimetallic particles was examined.
• The electronic state of Pt in the catalyst can be changed by the
concentration of Ru in the PtRu alloy.
Thank you for your attention!

3 材料化學 晶體與電子結構 劉如熹 0924 2020

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3 材料化學 晶體與電子結構 劉如熹 0924 2020

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台灣大學化學系．材料化學實驗室

Materials Chemistry Laboratory

Regular arrangements of the atoms in three dimensions

Point symmetry (點對稱)

Rotation axis (旋轉軸); n

n=1 n=2 n=3 n=4 n=6

Pentagons (x) Hexagons (o)

Translation symmetry operation

Mirror plane (鏡面）; m

(Symmetry respect to a plane)

Center of symmetry (對稱中心); 1

Point symmetry 之特性

此32個對稱群又稱為32 point group。

32 point group 代表32類不同之結晶幾何外觀對稱

Space symmetry (空間對稱)

Screw axis (旋移軸)

Translation Y/X of the unit cell edge in the

Glide plane (射移面)

axial glide a a/2 [010] [001]

diagonal glide n (a+b)/2 [001]

diamond glide d (a+b)/4 [001]

Crystal system and

Definition of axes, unit cell dimensions and angles for a general

Cubic Unit cell Characteristic symmetry

Tetragonal Unit cell Characteristic symmetry

Orthorhombic Unit cell Characteristic symmetry

Hexagonal Unit cell Characteristic symmetry

Trigonal (Rhombohedral) Unit cell Characteristic symmetry

（三方晶系；菱形晶系） a=b=c One threefold axis

Monoclinic Unit cell Characteristic symmetry

Triclinic Unit cell Characteristic symmetry

Trigonal a = b = c,α=β=γ≠900 One threefold

原始晶格; P 體心晶格; I 面心晶格; F 邊心晶格; (C, A, B)

230 space group

4-type of point symmetries (10 elements)

32 point groups (只是描述結晶之幾何外觀對稱)

73 space group (Lattice)

Lattice type (eg, P, I,….)

(b) For orthorhombic (含59個空間群）

(c) For Cubic (含36個空間群）

(d) For Monclinic (含13個空間群）

(e) For Triclinic (含2個空間群）

Powder X-ray Diffraction

Lattice planes, Miller indices,

Miller indices of planes in hexagonal crystals (h k i l)

<100> sets of directions are equivalent

Lattice type Rule for reflection to be

eg. -Fe: body centered cubic

Generation of Cu Kα X-rays. A 2p electron falls into the empty

2P3/2 移去 1S1/2 2S1/2 2P1/2 3S1/2 3P1/2 3P3/2

X-ray emission spectrum of a metal,

Bragg’s law : 2 d sin θ = n λ

(avoid collisions between air particles and

Cu Cu / Ni filter (The energy required to ionize

Table Filter for the Production of Monochromatic X-rays

Mo 0.711 Nb 0.0431 1.9 0.040 96.5

Zr 0.0673 2.7 0.044 96.8

Ni 1.659 Co 0.0158 0.6 0.014 98.7

Co 1.790 Fe 0.0166 0.7 0.013 98.9

Table X-ray Wavelength Most Useful in Diffraction Studiesa

2. 離子化偵測器 離子化室(ionization chamber)

（ionization detectors） 比例計數器

（solid state detectors） 閃爍計數器

3 材料化學晶體與電子結構劉如熹 0924 2020

3 材料化學晶體與電子結構劉如熹 0924 2020

2. 離子化偵測器離子化室(ionization chamber)

（ionization detectors）比例計數器

（solid state detectors）閃爍計數器