材料化學導論

Introduction to Materials Chemistry

“Materials Chemistry” Bradley D. Fahlman, 2nd Ed. Springer (電子書)

“材料化學” 梁碧峰，滄海書局

“Basic Solid State Chemistry” A. R. West, Wiley

“Solid State Chemistry, an Introduction” L. Smart; E. Moore, Chapman & Hall

國立中正大學化學暨生物化學系 廖儒修 教授
Department of Chemistry and Biochemistry, National Chung Cheng University
1
Chapter 1
Introduction to Materials Chemistry

Definition of “materials”
Substance having properties which make them useful in
machinery structures, devices and products.

Definition of “materials chemistry”

The study of the relationships between the arrangement of
atoms, ions, or molecules comprising a material, and its overall
bulk structural/physical properties. (Structure ↔ Property)

By this designation, common disciplines such as polymer,

solid-state, and surface chemistry would all be placed within
the scope of materials chemistry.
2
Important Daily Life Materials

* Metals
* Glass and Ceramics
* Polymers
* Composite materials
* Semiconductors
* Superconductors
* Magnetic materials
* Biomaterials
* Nanostructural materials
* Thin films

3
Metals and Alloys
The aluminum alloy used in the
production of beverage cans contains
manganese and is highly hardenable.
This means that when worked (or
hammered!), the aluminum becomes
harder or 'more resistant' to further
deformation.

shape memory alloys

4
Ceramics

Quartz
TiC 5
 Polymers and
molecular materials

Liquid Crystals

surfactants
Polymers generate color.
OLED (organic light-emitting diode)
6
Composites

glass-fiber/epoxy composite
aluminum oxide fibers
~ 12µm in diameter
7
Semiconductor Materials

8
Biomaterials

9
Classification of Materials MEM: MicroElectroMechanical

"lab on a chip"

10
Synthesis of Materials:
Top-down & Bottom-up.
(a) The top-down route is often used to
transform naturally occurring products
into useful materials. Representations
shown above include the conversion of
wood into paper products, as well as
certain golf ball covers.
(b) The bottom-up route of materials
synthesis is most prevalent. The
representation shown above is the
fabrication of plastics and vinyl found
in common household products and
automotive interiors, through
polymerization processes starting from
simple monomeric compounds
11
材
料
科
學
的
時
間
線

Figure 1.3. A 40-nm wide logo for NIST

(National Institute of Standards and
Technology), made by the manipulation of Co
atoms on a Cu(111) surface.

12
Characterization techniques for modern materials scientist:

* Photoelectron spectroscopy (PES)

* Auger electron spectroscopy (AES)
* Scanning electron microscopy (SEM)
* Transmission electron microscopy (TEM)
* Energy-dispersive spectroscopy (EDS/EDX)
* Secondary ion mass spectrometry (SIMS)
* Scanning probe microscopy (SPM)
* X-ray absorption fine structure (XAFS)
* Electron energy-loss spectroscopy (EELS)
● X-ray diffraction (XRD)

● Thermogravimetric analysis (TGA)

● Differential scanning calorimetry (DSC)

● Small-angle X-ray scattering (SAXS)

13
Example of Advanced Materials in Modern Society
Transparent Smart Windows

14
Timeline of Materials and Technological Discoveries

葫蘆 小鵝笛

15
Marvelous and Smart Materials
Smart materials or designed materials are
materials that have one or more properties that can
be significantly changed in a controlled fashion by
external stimuli, such as stress, temperature,
moisture, pH, electric or magnetic fields.

16
 Shape-memory Alloy (SMA)
An alloy that “remembers” its original, cold-forged (低溫鍛造)
shape: returning the pre-deformed shape by heating.

History
The first reported steps towards the discovery of the shape-
memory effect were taken in the 1930s. A. Ö lander discovered
the pseudoelastic behavior of the Au-Cd alloy in 1932.

Figure: Photographs of the shape-memory

effect at varying temperatures for a Ni–Ti wire.
17
Applications of Shape-memory Alloy

a 普通級 可以播完 注意：b 限制級 不能播完

18
How shape-memory alloy works?

Prof. Ainissa Ramirez at Yale University

19
 How shape-memory alloy works?

Figure: Unit cell representations of (a) the

CsCl structure of austenitic TiNi and (b) the
monoclinic structure of martensitic TiNi.

20
 How shape-memory alloy works?
Thermal Analysis is used to observe the phase-transition process.

DSC

Mf is the temperature at which the transition to martensite

completes upon cooling. As and Af are the temperatures at
which the transformation from martensite to austenite starts
and finishes. ξ(T) represents the martensite fraction.
21
 Photochromism
Photochromism is the reversible transformation of a
chemical species between two forms by the absorption
of electromagnetic radiation, where the two forms
have different absorption spectra.

video

22
Inorganic Photochromic Materials
AgCl and CuCl can be added to glass
materials to have photochromism.

Cl- + Ag+ + hv  Ago + Clo 變黑

Clo + Cu+  Cl- + Cu2+
恢復原色
Cu2+ + Ago  Cu+ + Ag+

23
Organic Photochromic Materials
Diarylethenes

Azobenzenes

24
 Electrochromism
Electrochromism is the phenomenon displayed by
some materials of reversibly changing color when a
burst of charge is applied.

Smart Toilet Window

25
How does electrochromism work?
WO3 + x Li  LixWO3 tungsten bronze

Semiconductor  Metallic Material

26
How does electrochromism work?

WO3 + x Li  LixWO3 tungsten bronze

WO3 + x H+ + x e-  HxWO3
Semiconductor  Metallic Material
27
Smart window using liquid crystals
liquid crystal
molecules with
polarity

Transparent Conductive
Oxide (TCO)

28
 Transparent Conductive Oxide (TCO)
導電玻璃
Common examples are n-type oxides such as:

ITO (Indium Tin Oxide)

FTO (Fluorine doped Tin Oxide)

Organic films are being developed using carbon

nanotube networks and graphene, which can be
fabricated to be highly transparent to infrared
light, along with networks of polymers such
as poly(3,4-ethylenedioxythiophene) and its
derivatives.

29
 Piezoelectricity
Piezoelectricity is the charge that accumulates in certain
solid materials in response to applied mechanical stress.
In other words, it means electricity resulting from pressure.

The first demonstration of the direct piezoelectric effect was

in 1880 by the brothers Pierre Curie and Jacques Curie.
30
How does piezoelectricity work?

perovskite
TiPbO3
31
 Aerogel (氣凝膠或空氣膠)
Aerogel is a synthetic porous material derived from a gel, in which
the liquid component of the gel has been replaced with a gas.

Aerogel was first created by Samuel Stephens Kistler in 1931, as a

result of a bet with Charles Learned over who could replace the
liquid in "jellies" with gas without causing shrinkage.

32
video
Synthesis of Aerogel

SiO2

Hydrolysis
Condensation
Polymerization
Supercritical Fluid Abstraction

wet gel, dried gel, glass (xerogel 乾凝膠)

33
 Silica aerogel, the lightest solid

• The world's lowest-density solid is a silica

aerogel (the latest and lightest versions of
this substance have a density 1 mg/cm³,
1/1000 as dense as water).

34
 World’s lightest metal (microlattice of Ni-P alloy)

In October 2016, HRL Laboratories was given the Guinness World Record for lightest
metallic structure. With a density (0.9 mg/cm³) that is 1/100 that of Styrofoam), HRL’s
material is a series of thin, hollow tubes made of a nickel-phosphorus alloy arranged in a
network called a microlattice. HRL constructs the airy microlattice by building a solid
plastic frame, bathing that plastic in a solution of nickel sulfate and sodium hypophosphite
for a few minutes to produce a thin alloy coating, and then dissolving the plastic with a
strong base, leaving only the hollowed-out metal structure. Compared with other light
materials, the microlattice stays intact when compressed, which means it can be used to
make things that need to be light yet strong, such as airplane wings and helmets.

C&EN ACS Feb 23, 2017

35
HRL: Hughes Research Laboratories
 Mechanical Strength of Aerogel

A 2.5 kg brick is supported by a piece of

aerogel weighing only 2.38 grams
36
 Applications of Aerogel

Aerogel has extremely low thermal conductivity (0.03 W/(m·K)),

which gives it remarkable insulative properties. Its melting point is
1200 °C.
37
 Thermoelectric materials
The thermoelectric effect refers to phenomena by which
either a temperature difference creates an electric potential
or an electric potential creates a temperature difference.
video

38
 History and How Thermoelectric Works?
These phenomena are known more
specifically as the Seebeck effect
(converting temperature to current),
Peltier effect (converting current to
temperature).
video

39
 Explanation of Seebeck and Peltier Effects

Hot end has more energetic electrons or holes

with longer mean free paths.

Energetic electrons (or holes) diffuse to the

cold end to develop an electric field.
Heat absorbed
-  from environment
Electric field
Electric field

 -
I

Seebeck effect Peltier effect 40

Applications of Thermoelectricity

Note: i is current, not electrons

The Seebeck effect is used in the thermoelectric generator.

The Peltier effect can be used to create a refrigerator which is
compact and has no circulating fluid.
(note: boiling point is liquid He is 4.222 K. How to reach T < 4.222 K?)

A thermocouple is a device consisting of two different conductors

(usually metal alloys) that produce a voltage, proportional to a
temperature difference, between either ends of the two conductors.
41
Thermoelectric materials
The figure of merit, ZT, of
the device is useful to
determine its suitability for
power generation or
refrigeration

a is the Seebeck coefficient

s is the electrical conductivity
l is the thermal conductivity
Semiconductors are better than metals.
The most widely studied TE material is Bi2Te3.
42
 Photovoltaics
光伏效應

Photovoltaics (PV) is a method of generating electrical power

by converting solar radiation into direct current electricity
using semiconductors that exhibit the photovoltaic effect.

43
How does photovoltaic cell work?

Note:
Light emitting
diode (LED) has
reverse process.

44
Conventional Silicon Solar Cells

In terms of power conversion efficiency (a ratio of light

energy in to electrical energy out) for silicon cells is in the
range of 20–25%.

Because silicon doesn’t absorb sunlight strongly (indirect

band gap), silicon cells contain a relatively thick layer of
silicon, which is brittle and therefore must be supported
on a rigid, heavy piece of glass, adding cost and limiting
applications.
45
 Dye-Sensitized Photovoltaic Cell
or Dye-Sensitized Solar Cell (DSSC)
Maximum certified efficiency: 11.9%

46
Inorg. Chem. 2005, 44, 6841 .
 The future of low-cost solar cells
Michael Grätzel

A key factor
contributing to the low
price of emerging
photovoltaics is the
ability to produce the
modules as large rolls The colors of the SwissTech Convention Center come from
of thin film via high- dye-sensitized solar cells integrated into the facade in
speed processes. panels made by Solaronix.

47
DSSCs can be sandwiched between panes of glass, turning
windows into electricity generators
One hot application is building-integrated photovoltaics. The idea is that
solar panels can be built into various parts of a building’s shell, not just the
rooftop, which is the preferred spot for silicon panels because they work
best in direct sunlight. DSSC panels, however, work well in diffuse light.
For that reason, thin sheets of translucent DSSCs can be sandwiched
between panes of glass, turning ordinary windows, skylights, and glass
facades into electricity generators.

48
 From Lab to Commercial Applications

One shortcoming of early designs is that the liquid electrolyte, typically an

organic solution of the iodide/triiodide (I–/I3–) redox couple, is corrosive,
volatile, and prone to leaking.

Seeking to improve the design, Northwestern University researchers replaced

the liquid electrolyte with a novel semiconducting inorganic solid: fluorine-
doped cesium tin iodide (CsSnI2.95F0.05).

49
 Organic Solar Cells
Maximum certified efficiency: 11.5% Conjugated polymer

fullerene

Light shining on an organic solar cell passes through transparent layers and stimulates
electron-hole pairs (e–/h+) in a photoactive layer (enlarged area is a bulk heterojunction). Upon
reaching an interface between a conductive polymer (pink, electron donor) and a fullerene
(yellow, electron acceptor), the pair splits. Positive charges hop via nanosized polymer
domains to one electrode, and negative charges migrate through the fullerene to the other one,
thereby generating electric current. 50
 Flexibility of Organic Photovoltaic Panels

Unfurl this thin, flexible organic

photovoltaic panel and charge your
phone or battery indoors or out, then
roll it back up for storage.

These thin organic solar-cell panels can be

integrated into cement and metal portions,
not just glass, of a building facade.
51
Quantum Dot Photovoltaics
Maximum certified efficiency: 11.3%

Light shining through the transparent electrode of a quantum dot solar cell onto
a photosensitive layer of dots leads to the formation of electron-hole pairs (e–/h+).
The charged particles separate and travel to their respective electrodes, thereby
producing electric current.

52
How does quantum dot solar cell work?

53
 Perovskite Solar Cells
Maximum certified efficiency: 29.1%
CaTiO3

Perovskite: ABO3

(CH3NH3)PbI3
Light passing through the transparent electrode (green) of a perovskite solar cell onto a
layer of a photosensitive perovskite material (blue) stimulates excitations called electron-
hole pairs (e–/h+). The charged particles separate and diffuse through the charge-
conducting layers to their respective electrodes, thereby generating electric current.
54
Perovskite solar cell

(CH3NH3)PbI3

55
Perovskite solar cells that can be installed almost anywhere

https://youtu.be/dqWuLtOH2v8
A major feature of perovskite solar cells is that they can be printed. At Panasonic, we have
developed a proprietary inkjet printer for printing perovskite solar cells. This has enabled the
manufacture of solar cells with customizable sizes and designs. They can even be
semitransparent. 56
Light-Emitting Diodes (LEDs)

The greatest breakthrough was realized in

the 1990s with the discovery of wide band
gap blue LEDs (GaN), making it possible
to create any color of light.
57
58
Organic Light-emitting Diodes (OLEDs)

ETL Organic emitter HTL

ITO: Tin-doped In2O3 conductive glass
59
Will the artificial leaf sprout to combat climate change?
Renewable sources of electricity will help us reduce climate-changing
carbon dioxide emissions, but our society will also need renewable fuels.
To find a renewable way to produce such fuels, some scientists have
developed technologies that use sunlight to split water to make molecular
hydrogen or reduce CO2 into hydrocarbons. These technologies face
significant engineering challenges to produce fuels efficiently and
economically.

60
C&EN, 2016, 94 (46), 32–38.
Turning sunlight into fuel

Light absorbed by semiconductors in the interior of the electrode causes charges to

separate. A catalyst on one side eases production of oxygen; on the other side, hydrogen
ions combine to generate hydrogen fuel. A thin layer of titanium dioxide protects the
electrode from being corroded by the electrolyte.
61
CO2 Emission Problem

62
CO2 Capture Materials

63
 Electrochemical CO2 Reduction

Photocatalytical
CO2 Reduction

64
 A Design of CO2 reduction

charge separation

h+

In Peidong Yang’s (UC Berkeley) hybrid reactor, man-made materials and biology
collaborate on artificial photosynthesis. Semiconductor nanowires absorb sunlight and
catalyze the reaction of water to form hydrogen ions. Bacteria living in the reactor take up
carbon dioxide and hydrogen ions and produce acetic acid. This is in turn fed to
engineered E. coli that can convert the acetic acid into valuable chemicals and fuels. 65
66
 Artificial leaf:
utilization of solar energy
Daniel Nocera (Harvard)

video

2 H2O  2H2 + O2
67
Nocera, D. et al Science 2011, 334, 645-648
 Making batteries fire-resistant with
solid electrolytes

The charred remains of a Li-ion battery that caught fire in the electronics bay
of a Boeing 787 airplane in January 2013 highlights the potential hazards of
these batteries, which use flammable liquid organic electrolyte solutions.

68
Energy Storage Materials and Devices (Batteries)

69
Disaster of Samsung

70
Battery: A device to convert the chemical energy of a
redox reaction to electricity.

Materials needed:
Cathode
Anode

Electrolyte
ionic but not electronic conductor

71
 Can solid electrolytes replace flammable organic liquids?

Li-battery

Most commercially available batteries use a liquid electrolyte because of its high ionic
conductivity. However, there is strong demand for the development of all-solid-state
batteries from the viewpoints of safety and stability.
72
 Challenge of New Ionic Conductors based on
Solid Electrolytes

In 2011, Ryoji Kanno of Tokyo Institute of

Technology, Yuki Kato of Toyota’s Battery
Research Division, and coworkers reacted Li2S,
GeS2, and P2S5 at high temperature. The team
reported that the product, Li10GeP2S12, or LGPS,
exhibited a Li-ion conductivity value of 12 mS
(millisiemens) per cm at 27 °C, the highest
conductivity value measured for a solid
electrolyte as of that date.

73
Nature Materials 2011, 10, 682–686.
 Ionic Conductivities of Various Electrolytes

LGPS
Li10GeP2S12

propylene carbonate

LiPF6/EC-PC
The new Li10GeP2S12 exhibits the highest lithium ionic conductivity (12 m S cm−1 at 27 °C)
of the solid lithium conducting membranes of inorganic, polymer or composite systems.
74
Nature Materials 2011, 10, 682–686.
 Best Ionic Conductor Based on Oxides
Li7La3Zr2O12 or c-LLZO
Substituting Ga3+ into this Li-La-Zr-oxide
(LLZO) compound stabilizes its cubic
structure. This material features Li-ion
vacancies and a low energy threshold for Li
ions to jump from site to site, making it a
good Li-ion conductor. LaO8 polyhedra are
blue; ZrO6 octahedra are green; the three
lattice positions occupied by Li+ are red,
orange, and yellow.

The garnet-type compound known as cubic Li7La3Zr2O12 or c-LLZO is thermally

and chemically stable—unlike sulfides; it does not require a controlled
environment for processing and has no sulfur so it cannot emit toxic hydrogen
sulfide. And it’s electrochemically inert over a wider voltage range than common
liquid electrolytes. In contrast to sulfide electrolytes, c-LLZO tends to exhibit a
maximum room temperature ionic conductivity of just 1–2 mS/cm, which is
relatively low but far greater than that of other oxides.
75
c-LLZO: 1–2 mS/cm

76
77
 Al
Li
Na

78
Sodium-Sulfur Secondary Batteries

79
A solid new approach to sodium batteries

Nanospheres of the ceramic

Na3Zr2(PO4)(SiO4)2 serves as the
solid electrolyte. Two ultrathin
polymer layers are added to avoid
dendrites.

Sodium-ion batteries are a promising low-cost alternative for Lithium-ion

batteries, because lithium is neither cheap nor plentiful, making Li-ion
batteries impractical for larger applications, such as storing wind and solar
power on a large scale.

A major issue of sodium batteries is its low energy density of 100 Wh/kg,
while lithium batteries have energy densities over 180 Wh/kg, and low
operating voltage.

(ACS Cent. Sci. 2017, DOI: 10.1021/acscentsci.6b00321). 80

Aluminum Batteries The battery operates through the
electrochemical deposition and
dissolution of aluminium at the anode,
and intercalation/de-intercalation of
chloroaluminate anions in the graphite,
using a non-flammable ionic liquid
electrolyte. The cell exhibits well-
defined discharge voltage plateaus
near 2 volts, a specific capacity of
about 70 mA h g–1 and a Coulombic
efficiency of approximately 98 per
cent. The cathode was found to enable
fast anion diffusion and intercalation,
affording charging times of around
one minute with a current density of
~4,000 mA g–1 (equivalent to
~3,000 W kg–1), and to withstand
more than 7,500 cycles without
capacity decay.

video

Dai, H. Et. al .Nature volume 520, pages324–328 (2015)

81
Metal–air Batteries (Li, Na, K, Mg, Ca, Al, Zn, Fe……)
A metal–air electrochemical
cell is an electrochemical
cell that uses an anode made
from pure metal and an
external cathode of ambient air,
typically with an aqueous
or aprotic electrolyte.

82
 Aluminium–Air Battery

Total reaction: 4Al + 3O2 + 6H2O → 4Al(OH)3 +2.71 V

台北 – 高雄 350 km
充電一次可走7趟

Other metals can be used in a similar way, such as lithium-air, zinc-air, manganese-air, and sodium-
air, some with a higher energy density. However, aluminium is attractive as the most stable metal. 83
Rust Batteries May Be the Cheapest Future Energy
Iron Air Battery

Form Energy 是包括比爾蓋茲（Bill Gates）投資成立的突破性能

源創投公司, 其鐵空氣金屬電池可在 2025 年前實現低廉持久儲能，
以鋰電池十分之一成本提供 150 小時電力。 (youtube)

84
Li–O2 (air) and Li–S batteries with high energy storage

85
Nature Materials 11, 19–29 (2012)
新里程碑：在最高峰時刻(2016某日)，德國
再生能源已滿足 95％ 全國用電！

自從2011年福島核災以後，
梅克爾即宣示將在 2022
年達成廢核目標。德國政
府正式通過再生能源法案
(RESA)的修正案，明訂
2025年再生能源發電量需
佔總用電量40~45%；2035
年目標進一步提高到
55~60%。

2015年台電系統發購電量為2,191億度，其中火力發電量占比達78.4%，其中燃煤
35.7%、燃油4.7%、燃氣35.1%、汽電共生2.9% (不含垃圾及沼氣)，再生能源占
比為4.2% (含水力及汽電共生中之垃圾及沼氣)，抽蓄水力1.4%，核能為16.0%。
86
2021年我國再生能源發電量共17,428,327
千度，其中慣常水力3,469,076千度，地熱
發電9,074千度，太陽光電7,968,746千度，
風力發電2,208,638千度，生質能發電
169,277千度，廢棄物發電3,603,517千度。

台電統計，2022年再生能源總共發出215億度電力，占整體發電占比8.6％。
87
Graphene
material of the future
Nobel Prize in Physics for 2010:
Andre Geim and Konstantin Novoselov

石墨烯（Graphene）是一種由碳原子以sp2雜化軌道組成六角型呈蜂巢晶格的平
面薄膜，只有一個碳原子厚度的二維材料。石墨烯從前被認為是假設性的結構，
無法單獨穩定存在，直至2004年，英國曼徹斯特大學物理學家安德烈·海姆和康
斯坦丁·諾沃肖洛夫，成功在實驗中從石墨中分離出石墨烯，而證實它可以單獨
存在，兩人也因「在二維石墨烯材料的開創性實驗」，共同獲得2010年諾貝爾
物理學獎。

石墨烯目前是世上最薄卻也是最堅硬的納米材料，它幾乎是完全透明的，只吸
收2.3%的光；導熱系數高達5,300 W/(m·K)，高於奈米碳管和金剛石，常溫下其
電子遷移率超過15,000 cm2/(V·s)，又比納米碳管或矽晶體（monocrystalline
silicon）高，而電阻率只約10-6 Ω·cm，比銅或銀更低，為目前世上電阻率最小
的材料。由於它的電阻率極低，電子的移動速度極快，因此被期待可用來發展
出更薄、導電速度更快的新一代電子元件或電晶體。石墨烯實質上是一種透明、
良好的導體，也適合用來製造透明觸控螢幕、光板，甚至是太陽能電池。

wikipedia 88
Graphene
material of the future

Future applications of graphene

video

graphene
transistor
Liao, L., Lin, Y.-C., Bao, M., Cheng, R., Bai, J., Liu, Y., Qu, Y., Wang, K. L., Huang, Y., &
89
Duan, X. (2010). High-speed graphene transistors with a self-aligned nanowire gate Nature
Graphene Tennis Racquet

90
 Applications of Graphenes
The idea is that the electronic skin patch - which
senses raised glucose and delivers a drug dose in
response - will remove the need for diabetics to
prick their finger.
(Hui Won Yun, Seoul National University)
Researchers at Stanford University have
successfully developed a brand new concept of
organic lighting-emitting diodes (OLEDs) with
a few nanometers of graphene as transparent
conductor. This paves the way for inexpensive
mass production of OLEDs on large-area low-
cost flexible plastic substrates, which could be
rolled up like wallpaper and virtually applied
anywhere you want.
91
 Graphene Chemistry
Pristine graphene and chemically
modified graphenes (CMGs) can react
with a variety of chemical substances.
These reactions have been applied to
modulate the structures and properties of
graphene materials, and to extend their
functions and practical applications.

92
Chemistry must be Green

趙奕姼 中央研究院化學所
93
 lb

Slide Courtesy Dr. Bob Peoples

 Materials

Waste

Slide Courtesy of Dr. David J. C. Constable, ACS Webinar

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