材料化學-白光發光二極體與量子點顯示元件

任課教師: 劉如熹 (臺灣大學化學系)

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 內容
白光發光二極體用之螢光粉原理、組成、製作與發展
量子點原理、合成與顯示元件

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白光發光二極體用之
螢光粉原理、組成、
製作與發展

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Colors Perceived

Color impression Wavelength (nm)

Red 630-780
Orange 600-630
Yellow 565-600
Green 500-565
Blue 435-500
Violet 380-435

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10 000 K Color Appearance
=
Color temperature

Kelvin (K)
0°C = 273 K
1000 K

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 sky
10 000 K
Light of the North

Sun in the Zenith

Natural light

6000 K
Daylight

In the afternoon
5000 K
Sunlight

Twilight
2000 K
Sunset
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 Mercury
4100 K
Neutral white

Ceramic discharge
Artificial lighting

3000 K
“Crisp” warm

White sodium
2500 K
“Cosy” warm

Sodium
1950 K
“Functional” orange
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 gives indication of:
Color Temperature appearance of light

warm ambience cool ambience

low color temperature high color temperature

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Color Temperature

2000 K 3000 K 4000 K

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Color Rendering index; Ra (演色性)

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Color Temperature & Color Rendering

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 The Nobel Prize in Physics 2014
Nobel Prize in Physics 2014

Isamu Akasaki Hiroshi Amano Shuji Nakamura

赤崎勇 天野浩 中村修二

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Taipei 2017 Universiade 8/19-30/2017
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Phosphors for Solid State Lighting-
White Light-emitting Diodes

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GaN Blue Chip/YAG for WLEDs

Nichia

(light)

(Phosphor)

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Y3Al5O12；Yttrium Aluminum Garnet ( YAG )

Y(X)
X3(A3B2)O12

Al；Tetrahedral(A) Cubic (I a -3 d)

Engrgy transfer

Al；Octahedral(B)
H A A H

H H A H
H
H: Host (Y3Al5O12)

A Activator (Ce3+)
A: H A H H
H H A
A H

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Ce3+
5d

4f

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Packaged LED Cost

Source: USA DOE, LED report 2009; Stanley Myers, SEMI,

“Components of Supply Chain Excellence,” SSL Workshop,
Fairfax VA, April 21, 2009

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 LED industry chain in Taiwan
Epistar
Equipment Lextar
Everlight
CYT、WEC、Single
Unity Opto Technology
Well、Fittech、
Lumileds (Shanghai)
Wecon Rapitech
Mitsubishi (Japan)
Merck (Germany)
Substrate Epi-Wafer Packaging Application

SAS、Crystal Epistar、Lextar、Huga 、 LiteOn、Everlight、 IST、Led Light、

Tekcore、GPI、Arima、 Kingbright 、Harvatek、 Chiphope、JE、Color
Wise、TXT、 Bright、Unity、AOT、
Touchtek、HPO、VPEC、 Stars、AKSLEN、Conary
Wafer Works Nan Ya VTERA、Tyntek、 Oasis、Optotech、Bright 、Genhome、Giant
View、Edison、Prolight、 Bright、Laster Tech、
Hightlight、Lumitek
Ligitek
Para Light

Sorting & Module Lead frame

YTEC、MPI、 I-Chiun、 -China glaze

Chroma Kenly、BCC
-Chi Mei
Source：PIDA, 2010/9
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 White LEDs: Approaches

(Ref: http://www.lumileds.com)
Three Methods of Generating White Light from LED

R + G + B LEDs Blue LED + Yellow Phosphor UV LED + RGB Phosphors

(460-480 nm) (380-400 nm)

 Dynamic color  Simple to create white White point determined by

 Excellent color rendering  Good color rendering phosphors only
 Excellent color rendering
 Large color gamut
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2014

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螢光粉製作方法

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Solid state reaction

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Nitrogen Gas Pressure Syst
- 2300 oC - 0.95 MPa (9.5 atm)

1900 ℃ 3 hours
@ 0.90 MPa N2

SrSi6N8
SrSi6N7.95O0.05

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 檸檬酸鹽凝膠法合成YAG粉體

金屬硝酸鹽化合物 檸檬酸(citric acid)

溶於水中
以乙二胺調整
pH值至10
金屬錯合物水溶液
加熱除去多餘水分，直至
形成黃褐色凝膠前驅物
凝膠前驅物(gel precursor)
於300℃之空氣
中熱分解2小時

HO M 黃灰色粉末
+ H H
O 於1000℃之空氣中煆燒
H N N H
OH 24小時
HO CH2CH2
O H H 黃色粉末
M
OH H N N H HO + 於1500℃之空氣中燒結
O CH2CH2 O
24小時
O
HO 黃色粉末
OH H H 於1500℃之氮氫(95%/5%)混合
OH H N N H
+ 還原氣體中退火6至12小時
O CH2CH2
M 產物
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 Citrate Gel

SEM

Solid State Citrate Gel

-鈰摻雜釔鋁氧石榴石微細螢光粉粉末的製備方法
(台灣發明專利號碼1235231)

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白光發光二極體之發展

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CCFL LED

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http://digiphoto.pixnet.net/blog/post/24444745
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 Competition of lighting equipments
Competition of lighting
equipments
Color
temperature (K)
2,500~3,000 3,000~10,000 3,000~10,000
Response time ＜100 ms ＜60 ms ＜0.001 ms
Luminescence
Heat Gas cold
Life time ~1,000 h ~ 5,000 h ~50,000 h
Electricity 100 % Saving 50 % Saving 90 %
consumable

Impact Easy broken Easy broken Not easy broken

Disadvantages Electricity consumable、 Mercury contamination、 High price
short life and easy easy broken
broken

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 Black Pearl-Nikkei
Taiwan LED Lighting Architecture (Nichia,7000sets)

Taipei Municipal Social Education Hall

(LumiLeds, 1W, 25 lm/W) MiramarHotel
TIR

NSC Science Technology Building

(Nichia, 1W, 20 lm/W)

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 Everlight
Ceiling

(~ 120 W/lamp; 45 LEDs; 3W/LED)

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量子點原理、製作與顯示元件

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1.量子點原理

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 ⊙ 多電子原子中軌域填入的次序

Energy level scheme for atoms

1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
6s 6p 6d
7s 7p

7N 1s22s22p3
1s 2s 2p
1s22s22p4
8O
1s 2s 2p
1s22s22p5
9F 1s 2s 2p

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The Molecular Orbital Model (MO)

– Molecular orbitals have many of the same

characteristics as atomic orbitals

– Two of the most important are :

(1) they can hold two electrons with opposite
spins and
(2) the square of the molecular orbital wave
function indicates the electron probability

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e.g. The combination of hydrogen 1s atomic orbitals to form
molecular orbitals

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於分子中只有分子軌域可以 ∵兩個分子軌域間的
被電子占據，表示氫原子之 電子恰分布兩原子核
1s原子軌域不再存在，因為 的中心線 (即核間軸)
氫分子將有新的軌域生成

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‧ MO1 之能階比 H 原子之 1s orbital 還低，而MO2則
比單一氫原子的 1s 軌域高

(a) => 電子填入氫分子之MO1orbital (較氫原

子之能階低)，有利於分子之形成，即有利於
bonding (鍵結) → 電子為兩原子核共享

(b) => 當電子分布在較高MO2能階時，則稱為

antibonding (反鍵結) → 電子偏向原子各自獨立

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A molecular orbital energy – level diagram for the H2 molecule

Molecular electron configuration for H2 = s1s2

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⊙ Bond order = ( number of bonding electrons
–– number of antibonding electrons ) / 2

– Bond order is an indication of bond strength, because it

reflects the difference between the number of bonding
electrons and the number of antibonding electrons,
which in turn reflects the quantity of energy released
when the molecule is formed from its atoms.

– Larger bond order → shorter bond length →

greater bond strength

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 e.g. Bond order ==> H2 , H2
H2-

B.O. = 2 – 0 = 1 B.O = 2 – 1 = 1/2

2 2

H2 較 H2 Stable，且前者 bond strength 為後者之2倍

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e.g. He2 是否 stable ?

B.O = 2 – 2 = 0
2

∴ He2 unstable

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Bonding in Homonuclear Diatomic Molecules
e.g. Li2
Li electron configuration : 1s2 2s1

The relative sizes of

the lithium 1s and
2s atomic orbitals

∵ 1s 軌域太小 => 1s 軌域並未重疊 => 未參與鍵結

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Figure 14.34 : Li2 energy-level diagram

∵ B.O. = (2 – 0)/2 = 1
Li2 => stable molecules ( 但事實上常溫常壓下，許
多Li 原子是互相鍵結在一起，
而以固體之型式存在 )

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e.g. Be2 ( 4 個價電子)

B.O. = (2 – 2) / 2
=0

∴ Be2 unstable

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 物體如何導電—Band Theory

電子未填滿

e- e- 能帶
E = = (Energy Band)
(能階) e- e -

e- e-

電子填滿
1H 2H 3H NH
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 Intrinsic semiconductors

× Band structure of
Semiconductor (Si) band
Empty band→conduction
×
× ×
σ*band

Si1 Si2
1
2
σband
3s23p2 sp3 Valence band →full
4個價電子 hybridization

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 金屬、半導體、絕緣體的導電模式

金屬

半導體 絕緣體
e-

e-
e-
e- Phonon
聲子
不需給予能量 需給予能量0.5~3 eV 需給予能量≧6 eV
(無能階差) (能階差0.5~3 eV) (能階差≧6 eV)
導電性佳 導電性一般或不良 導電性不良或不導電

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Ref: Quantum Dots conference 2014-Dr. Jonathan Owen

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Ref: Quantum Dots conference 2014-Dr. Jonathan Owen
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Quantum dots

ℎ2𝜋2
𝐸𝑛 = 𝐸𝑔 +
2𝜇𝑅2
En = Band gap of quantum dots
Eg = Band gap of bulk semiconductor
h = Planck’s constant
R = Radius of quantum dots
m = Reduce mass of exciton

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Ref: Quantum Dots conference 2014-Dr. Jonathan Owen

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Ref: Quantum Dots conference 2014-Dr. Jonathan Owen

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 Perovskite
Mineral
Cubic structure CaTiO3
A X
B

ABX3 Photodectors
A= Cs+,CH3NH3 + (MA+),

CH(NH2)2 (FA+)
B = Pb, Sn
X = Cl, Br and I Solar cells

Light emitting diodes

Ref : Nano Lett., 2015, 15, 3692.

Ref : J. Mater. Chem. A, 2015, 3 , 9011.
Ref : Nature Nanotechnology, 2012, 7, 363.

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2. 量子點製作

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3. 量子點之重要

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Why we need to use perovskite quantum dots in LEDs?

Ref : https://www.cnet.com/how-to/should-you-be-worried-about-8k-tv/

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 PL

LCD LCD(LED)
(flourescent) Q-LCD

EL

OLED QLED

Ref : Adv. Mater. 2017, 1607022.

Ref: Nat. Mater, 2015, 14, 454.

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 QLED

Ref. https://www.youtube.com/watch?v=CxwXK
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 On Chip type Film type

Ref: JMCC., 2013, 7, 9019

Advantages: Advantages:
 Low cost
 Commercial product (3M QDEF)
 Easy fabrication
 Highly stability
 Mini display (cell phone, tablet,
flash light) Disadvantages:
Disadvantages:  Only for bigger display (TV,
 Photo stability Laptop)
 Thermal stability  High cost

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 Challenges :

(1) Blue pump intensity on chip

(photo stability, thermal
stability)

(2) Compatibility between matrix

material and QDs

(3) O2 and Water effect

Solutions :

(1) Fabrication type (Remote type)

(2) Quantum dots nanocomposite

(3) Barrier film (polymer)

Ref : 2016 Phosphor Global Summit OSRAM company report
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 Organic
Fluorescence OLEDs Advantages:
Materials  Commercial product
(LG TV, Sumsung Display)
FWHM
 Highly luminescence
120~150 nm blue device
Ref: AAPPS BULLETIN. 2016 , 26 Disadvantages:
 High cost
Quantum dots Ref : Chem. Mater.,2006, 18, 5789.
 Lifetime
FWHM
20~40 nm QLEDs Advantages:
 High NTSC color gamut
 low cost
 Good Lifetime
Disadvantages:
 Toxic QDs (CdSe/ZnS)
 Immature technology
Ref: ACS nano., 2013, 7, 9019.

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 Various QDs
Cd-QDs InP-QDs Perovskite QDs
CsPb(Br1-x/Ix)3
x=0

Normalized Intensity (a.u.)

x = 0.2
x = 0.4
x = 0.6
x = 0.8
x=1

500 550 600 650 700 750

Wavelength (nm)

Advantages: Advantages: Advantages:

 Narrow emission  Non-toxic  Narrow emission
wavelength wavelength
 Highly Quantum efficiency
 Highly stability  Highly Quantum efficiency
 Highly stability Disadvantage:
Disadvantage: Disadvantage:  Low stability
 Toxic  Lowly quantum efficiency
Ref. Chem. Commun. ,2008, 2106

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 White light LEDs Organic Light emitting diode (OLEDs)
Q-LED (PL) QLED (EL)
Blue chip

White light

Green light and red light

materials and silicon gel

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 Q-LED (PL)

β-SiAlON
green phosphor
f-d transition
50~55 nm

K2SiF6:Mn4+
red phosphors
2E -4A transition
g 2g

~50 nm

Quantum dots
CB-VB transition
20~40 nm
Ref: Nat. Mater, 2015, 14, 454.
Ref: Nano Lett., 2015, 15, 3692.

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QLED (EL)
OLED Advantages:
 Commercial product
(Sumsung TV)
 Highly luminescence
blue device
Disadvantages:
 High cost
Ref : Chem. Mater.,2006, 18, 5789.
 Lifetime

QD-LED Advantages:
 High NTSC color gamut
 low cost
 Good Lifetime
Disadvantages:
 Toxic QDs (CdSe/ZnS)
 Immature technology
Ref: ACS Nano., 2013, 7, 9019.

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未來展望

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Micro and Mini LEDs

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MicroLED - self-emitting display
technology that uses very small
LED subpixels.

A microLED pixel is ~3-20 μm in diameter that

is capable to generate about 1mW with a light
intensity of 300 W/cm3.

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 Display technologies

 Electric circuit trigger transfer of

molecule.
 Color filter + backlight source powers
LCD

each pixel
 RGB mixture create colors

 Electric current powers

OLED

OLED
 OLED emit light from its
organic thin film
microLED

 Miniature LED array

 1 microLED = 1 pixel
 Smaller module  brighter image
quality and faster response time

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Comparative performance of MicroLED
Parameters LCD OLED MicroLED

Technology Type Backlight/ Self Self emitting

LED emitting

Contrast 5,000: 1 infinity infinity

Life span medium medium long term

term term

Reaction time ms μs ns

Work T 40-100°C 30-85 C 100-120°C

Cost low mid-range high

Energy high mid-range low

consumption

Visible angle low mid-range high

PPI wearable 250 max 300 max >1500

PPI VR 500 max 600 max >1500

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MicroLED assembly
Massively Parallel Transfer Arrays Monolithic Integration
“Pick-and-place”

backplane
‘picker’

epiwafer

epiwafer microLED array

backplane

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MicroLED market

http://www.ecouterre.com/

http://www.ledinside.com/

https://www.linkedin.com/pulse/virtual-augmented-
reality-vrar-change-workplace-forever-onesto

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 Ref.: USA DOE, LED report 2009; Stanley Myers, SEMI, “Components of
Supply Chain Excellence,” SSL Workshop, Fairfax VA, April 21, 2009.

Evolution of Fluorescent-materials
Market
Applications

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Published books

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