ORGANIC COMPOUNDS FOR VISUALISATION
TECHNOLOGY
1. MARKET OF DISPLAYS AND SCREENS
2. LIQUID CRYSTALS
3. ORGANIC LIGHT EMITTING DIODES
1. MARKET OF DISPLAYS AND SCREENS
CRT LCD (TN, STN, TFT, FLC, AFLC) OLED QLED
PRINCIPLE APPLIED VOLTAGE CHANGES LIGHT IS EMITTED WHEN AN LCD TECHNOLOGY WITH
TRANSPARENCY OF LC FOR APPLIED VOLTAGE EXCITES BACK LIGHTENING IMPROVED
POLARISED LIGHT BY CHANGE ORGANIC MATERIAL BY QUANTUM DOT
OF ORIENTATION OF MOLECULES TECHNOLOGY
THICKNESS 40-60 cm 1-3 cm 3 mm 1 cm
ENERGY CON- 180 W 50 W (LIGHT OF EXTERNAL <10 W (WHOLE LIGHT IS USED) SLIGHTLY HIGHER
SUMPTION SOURCE IS FILTERED)
VIEWING UP TO 180° FROM 50° TO 160° (DEPENDS ON 180° (LIGHT IS IRRADIATED IN SLIGHTLY LOWER COMPARED
ANGLE TECHNOLOGY) ALL DIRECTIONS) TO OLED
SCREEN SIZE LIMITED LIMITED; 19“ CRT ≈ 17“ LCD EASY EXTANDABLE
LIFETIME <50,000 h >50,000 h ~ 100,000 h
DRAWBACKS IRRADIATION COMPLICATED TECHNOLOGY: +: WARM NATURAL, BRIGHT +: EVEM MORE VIVID
OSCILLATION EXTERNAL LIGHT, POLARISERS, COLOURS, FAST RESPONSE, COLOURS, HIGHEST
OF IMAGE DIFFUSERS; MEMORY EFFECT HIGHEST CONTRAST, PERFECT BRIGHTNESS
BLACK (PIXEL SWITCH OFF)
PRICE MEDIUM LOW HIGHER COMPARABLE TO OLED
1. MARKET OF DISPLAYS AND SCREENS
PLASMA TV
Plasma television screens are essentially an array of cells (pixels, composed of three sub-pixels, corresponding to the
colors red, green and blue). Gas (neon, argon or xenon) in a plasma state (high voltage applied to low pressure gas
chambers) is used to react with phosphors in each sub-pixel to produce colored light (red, green, or blue). The same
phosphors used in plasma television technology are used in conventional cathode ray tube (CRT). However, the viewer
gets more vivid, dynamic colors than expected. Each subpixel is individually controlled by advanced electronics to
produce 16.77 million different colors. Moreover, these "perfect images" that are easily viewable in a display that is less
than six inches thick. Viewing angle 160°
Drawbacks: not perfect gray tones, not exact colours, slower response, medium price, high energy consumption (300-
500 W).
,
H3C
2. LIQUID CRYSTALS CH3
CH3
CH3
CH3
O
HISTORY H
O
1888 Friedrich Reinitzer (1857-1927): Cr 148 N 179 I
cholesteryl benzoate
1922 Georges Freidel: classification of crystalline phases (nematic, smectic, cholesteric)
1906-1924 Vorländer: polymorfism
up to 1965 academic interest only
1968 1ST display
1971 1ST display based on crossed nematics (TN-LCD)
1985 1ST pocket TV based on TFT-TN-LCD (Seico)
1987 1ST display based on super-TN-LCD
1991 Nobel Prize in Physics to Pierre-Gilles de Gennes "for discovering that methods developed for studying
order phenomena in simple systems can be generalized to more complex forms of matter, in particular to
liquid crystals and polymers"
2002 29-30´´ TFT screens (Phillips)
2002 prototype of AFLC screen (Citizen, Casio, Toshiba)
2003 production of LCD: 30 mlds pieces
2. LIQUID CRYSTALS
CRYSTALLINE PHASE – three-dimensionally ordered
LIQUID CRYSTALLS (MESOPHASE) – partially ordered (ordered fluid)
LIQUID PHASE – disordered
CLASSIFICATION
• LYOTROPIC – solvent dependent (soaps and other surfactants) – form ordered micelles, membranes, etc.
• THERMOTROPIC – temperature dependent OC8H17
- CALAMITIC (rod like)
H
- DICSOTIC C5H11O C
- BANANA-SHAPED N C6H13 C8H17O OC8H17
O O
O O
O O
O
O
O O
C8H17O O
O O O O
N N O
OC8H17
RO OR
OC8H17
Acc. Chem. Res. 2001, 34, 845.
2.
LIQUID CRYSTALS
2. LIQUID CRYSTALS
PHASE TRANSITIONS OF ROD-LIKE COMPOUNDS FORMING LIQUID CRYSTALS
Molecules in fixed Smectic: Molecules are fixed Molecules are able Molecules can
positions, unable within the layers to tumble rotate and move
to rotate SmA: layers can slip
SmC: all molecules in layer can tilt
LC: molecules keep they orientation along a vector,
molecules can rotate
Acc. Chem. Res. 2001, 34, 845.
2. LIQUID CRYSTALS
PHASE TRANSITIONS OF ROD-LIKE COMPOUNDS FORMING LIQUID CRYSTALS
Acc. Chem. Res. 2001, 34, 845. Phase transitions observed by DSC
2. LIQUID CRYSTALS
PHASE TRANSITIONS OF ROD-LIKE COMPOUNDS FORMING LIQUID CRYSTALS
Examples
enabled by cross-couplings
Acc. Chem. Res. 2001, 34, 845.
2. LIQUID CRYSTALS
PHASE TRANSITIONS OF ROD-LIKE COMPOUNDS FORMING LIQUID CRYSTALS
Examples
0V 50 V/60 Hz, 207 °C
O
O S
O OC12H25
C10H21O
O
O
H
Cr 118 SmC* 208 I
2. LIQUID CRYSTALS
PHASE TRANSITIONS OF ROD-LIKE COMPOUNDS FORMING LIQUID CRYSTALS
Chiral smectic C phase
Acc. Chem. Res. 2001, 34, 845.
2. LIQUID CRYSTALS
PHASE TRANSITIONS OF ROD-LIKE COMPOUNDS FORMING LIQUID CRYSTALS
Chiral smectic C phase
PS
PS
E<0 E=0 E>0
ferroelectric arrangement antiferroelectric arrangement ferroelectric arrangement
By applying an electric field across the film, LC can be switched between two opposite tilt orientations (i.e., between
+ and -) to give an ON/OFF light shutter between crossed polarizers.
Ability to switching is achieved by use of chiral dopant, allowing spontanneous polarisation
X = F, NO2
Acc. Chem. Res. 2001, 34, 845.
2. LIQUID CRYSTALS
PHASE TRANSITIONS OF ROD-LIKE COMPOUNDS FORMING LIQUID CRYSTALS
Chiral smectic C phase
Molecular origin of spontanneous polarisation:
conformational asymmetry
Acc. Chem. Res. 2001, 34, 845.
2. LIQUID CRYSTALS
TN-LCD
2. LIQUID CRYSTALS
2. LIQUID CRYSTALS
TFT-LCD
HISTORY
3. ORGANIC LIGHT EMITTING DIODES
1990 Cavendish:
1st LEP (light emitting polymer) device
Emitting yellow-green light
3. ORGANIC LIGHT EMITTING DIODES
CONSTRUCTION AND PRINCIPLE
1 pixel:
Combination of three slots with red, blue and green colours
electron injection
hole injection electroluminiscence
Cathode
Al/Ca or LiF
ITO anode
indium tin oxide
HTM
(donor) emitter
ETM
(acceptor)
Injected hole and electron recombine to form exciton (life time
in nanoseconds), followed by its photonic decomposition
Chem. Mater. 2004, 16, 4556.
3. ORGANIC LIGHT EMITTING DIODES
CONSTRUCTION AND PRINCIPLE
3. ORGANIC LIGHT EMITTING DIODES
CONSTRUCTION AND PRINCIPLE
ITO
_____
4.8 eV
3. ORGANIC LIGHT EMITTING DIODES
FACTORS:
Efficiency of electron/hole injection from electrodes
Charge balance
Spin multiplicity of electronically excited state (1S – fluorescence, 3T – phosphorescence)
Emission quantum yield
Light output coupling factor
INVESTIGATED CHARACTERISTICS:
Electroluminscence wavelength (nm)
Current efficiency (cd/A)
Luminance (l/W)
Quantum efficiency (%)
Chem. Mater. 2004, 16, 4556.
3. ORGANIC LIGHT EMITTING DIODES
SPIN MULTIPLICITY OF ELECTRONICALLY EXCITED STATE
LUMO
HOMO
ground state singlet triplet
excited states
radiative decay thermal decay
(radiative decay is forbiden)
Statistically one singlet and three triplets are formed for each four electron-hole pairs injected into the recombination
interface of the PPV device. The triplet decay path does not produce light emission. The outcome of this quantum
ruling is that from the outset, the device is limited to 25% efficiency.
Chem. Mater. 2004, 16, 4556.
3. ORGANIC LIGHT EMITTING DIODES
EMITTERS:
• Linear conjugated polymers (Light-emitting polymers - LEPs)
• Small molecules (SMOLEDs)
3. ORGANIC LIGHT EMITTING DIODES
POLYMERS
EXAMPLES
Co-polymers to PPV to tune color
Green color efficiency 16 lm W -1
3. ORGANIC LIGHT EMITTING DIODES
POLYMERS
3. ORGANIC LIGHT EMITTING DIODES
POLYMERS C8H17 C8H17
EXAMPLES
EL 446 nm
Poly(dialkylfluorene)s (enabled by Suzuki coupling) 2
1600 cd/m
0,02%
n
blue
n
C8H17 C8H17
EL 465 nm
blue
blue
blue
yellow
3. ORGANIC LIGHT EMITTING DIODES
SMALL MOLECULES
EXAMPLES
CH3 OMe CH3
N N
(CH3)3C C(CH3)3
N N
H3C MeO H3C
blue-violet EL: 444 nm
N
O
3 Al
Alq3 green
Red EL: 680 nm
Chem. Mater. 2004, 16, 4556.
3. ORGANIC LIGHT EMITTING DIODES
EXAMPLES O O
SMALL MOLECULES
PEDOT =
Al/Ca 2 S n
10500 cd/m
sample
PEDOT/PSS 0,45% at 16 V
ITO S
S N
S O
3 Al
S
SO2 Alq3
2
red EL 4600 cd/m
1,6%
Mg/Al H3C N
Alq3 N N N
BCP
sample CH3
NPB BCP
ITO
O N O
CH3
N N
NPB
3. ORGANIC LIGHT EMITTING DIODES
EXAMPLES SMALL MOLECULES
4
Normalized EL intensity (arb. u.)
10
(a) 1.0 (b) 15
Current density (mA/cm )
3
10
2 Applied voltage 10
2 0.8 11 V 5
10
12 V 0
10
1 0.6 13 V 400 600 800
14 V
0
10 0.4 15 V
-1
10
0.2
-2 Alq3 / -NPD
10
Alq3 / H2T26N 0.0
-3
10
0 5 10 15 300 400 500 600 700 800
Applied voltage (V) Wavelength (nm)
(c)
-3.0 eV Ca
- -3.1 eV N
O
H2T26N (i) 3 Al
(ii) Alq3
ITO Alq3
+ +
-5.8 eV -5.7 eV
Synth. Met. 2016, 211, 84-86.
3. ORGANIC LIGHT EMITTING DIODES
OLED MANUFACTURE
Ink-jet deposition of solution
Red: rhodamine dopped PPV
Green: PPV
Blue: poly(dialkylfluorene)
Flattening by spinning, solvent evaporation
Layers about 100 nm
3. ORGANIC LIGHT EMITTING DIODES
OLED PRODUCTION
Handy displays: Motorola, Samsung (majority), Sony Ericsson (Z610i), Nokia
7900 Prism, Nokia 8800 Arte, Kodak NuVue (camera displays)
TV-set XEL-1 (SONY) – 28’ OLED commercially available from December 2007,
cost 2,000 USD
2024: 55’ TV-set from 1,000 EUR
