《微纳米加工及应用》教学课件Self-assembly

Self-assembly微纳米加工及应用OutlineBasic

concepts生物体系中的自组装Tobacco

mosaic

virus

(TMV)DNA人工自组装分子自组装单层膜：烷基硫醇LB膜纳米晶体的自组装：金属纳米晶

辅助自组装（assistedself-assembly）模板辅助的自组装外场辅助的自组装：静电场，

交变电场，磁场自组装在纳米电子学中的应用单电子晶体管单分子器件结束语OutlineBasic

concepts生物体系中的自组装Tobacco

mosaic

virus

(TMV)DNA人工自组装分子自组装单层膜：烷基硫醇LB膜纳米晶体的自组装：金属纳米晶 辅助自组装（assistedself-assembly）模板辅助的自组装外场辅助的自组装：静电场，

交变电场，磁场自组装在纳米电子学中的应用单电子晶体管单分子器件结束语Overview

Self-assembling

processes

are

common

throughout

nature

andtechnology.

They

involve

components

from

the

molecular

(crystals)

to

theplanetary

(weather

system)

scale

and

many

different

kinds

ofinteractions.

The

concept

of

self-assembly

is

used

increasingly

in

manydisciplines,

with

a

different

flavor

and

emphasis

in

each.The

definition

of

SA

Self-assembly

is

the

autonomous

organization

of

components

intopatterns

or

structures

without

human

intervention.-G.M.

whitesides,

B.

Grzybowski

Self-assembly

is

a

spontaneous

and

reversible

process

that

bringstogether

in

a

defined

geometry

randomly

moving

distinct

bodiesthrough

selective

bonding

forces.-Serge

Palacin,

Renaud

demadrillHere,

we

limit

the

term

to

processes

thatInvolve

pre-existing

componentsCan

be

controlled

by

proper

design

of

the

componentsOutlineBasic

concepts:Definition

of

Self-assembly 生物体系中的自组装Tobacco

mosaic

virus

(TMV)DNA人工自组装分子自组装单层膜：烷基硫醇LB膜纳米晶体的自组装：金属纳米晶

辅助自组装（assistedself-assembly）模板辅助的自组装外场辅助的自组装：静电场，

交变电场，磁场自组装在纳米电子学中的应用单电子晶体管单分子器件结束语Tobacco

mosaic

virus感染了烟草花叶病毒的体系，植物叶子上表现出病毒引起的马赛克；烟草叶上坏死的局域部分.Structure

of

TMV烟草花叶病毒的结构特征：长约300nm，直径约18nm，包含2130个表层蛋白分子和由6400个氨基酸分子组成的RNA。Structure

of

TMVSA

of

TMVOutlineBasic

concepts生物体系中的自组装Tobacco

mosaic

virus

(TMV)DNA人工自组装分子自组装单层膜：烷基硫醇LB膜纳米晶体的自组装：金属纳米晶 辅助自组装（assistedself-assembly）模板辅助的自组装外场辅助的自组装：静电场，

交变电场，磁场自组装在纳米电子学中的应用单电子晶体管单分子器件结束语DNAWatson

and

Crick

with

DNAmodel1953年发现1962年诺贝尔奖在DNA分子结构构建方面，威尔金

斯和富兰克林提供了DNA衍射图谱；查哥夫发现了A的量总是等于T的量、C的量总是等于G的量。沃森和克里克在此基础上提出了DNA分子的双螺旋结构模型。Structure

of

DNAReplication

of

DNAReplication

of

DNA:

SALessons

from

natural

SAManipulationSelf-assemblyOutlineBasic

concepts生物体系中的自组装Tobacco

mosaic

virus

(TMV)DNA人工自组装

分子自组装单层膜：烷基硫醇

LB膜纳米晶体的自组装：金属纳米晶 辅助自组装（assistedself-assembly）模板辅助的自组装外场辅助的自组装：静电场，

交变电场，磁场自组装在纳米电子学中的应用单电子晶体管单分子器件结束语SAMsSelf-assembled

monolayers

(SAMs):

SAMs

are

ordered

molecularassemblies

that

are

formed

spontaneously

by

the

adsorption

of

asurfactant

with

a

specific

affinity

of

its

headgroup

to

a

substrate.Different

systems

of

SAMsDefine

the

individual

SAM-systems

byusing

the

headgroup-substrate

pair

R-SH

(R-SAc

or

disulfide):

Au,Ag,

Cu,

Pd,

Ni,

Pt

Silane-based

SAMs:

on

surfacewith

–OH

groupsR-NC:

Au,

Pt,

PdR-CN:

Au,

CuR-NH2:

Au,

Ag,

PtothersPreparation

of

thiols

SAMSSolution

depositionSubstrateGas

phase

depositionThiol

moleculesFormation

of

a

SAMSTM

image

of

a

SAM7

x7nm2

STM

image

of

C6

SAM( 3

x 3)R30°

overlayerLangmuir,

17(2001):,

4919Characteristics

of

this

SAMS

in

three-fold

hollow

siteProton

loss

on

adsorption

(SH S-)(硫醇30º

tilt

to

the

normal硫醇盐）distance

between

attachment

sites

=

5

Ådiameter

of

n-alkyl

chains

=

4.6

ÅAu-S

band

strength

=

~40kcal/moleVan

der

Waal

forces

between

–CH2-

groups

=

~1.5kcal/moleN-alkyl

chains

adopt

a

trans

zig-zag

structureAt

room

temperature,

only

a

few

gauche

defects

in

outermost

–CH2-Basic

concepts生物体系中的自组装Tobacco

mosaic

virus

(TMV)DNA人工自组装分子自组装单层膜：烷基硫醇

LB膜

纳米晶体的自组装：金属纳米晶 辅助自组装（assistedself-assembly）模板辅助的自组装外场辅助的自组装：静电场，

交变电场，磁场自组装在纳米电子学中的应用单电子晶体管单分子器件结束语OutlineLB

techniqueA

schematic

of

a

Langmuir

Blodgett

trough:

1.

Amphiphile

monolayer2.

Liquid

subphase

3.

LB

Trough

4.

Solid

substrate

5.

Dipping

mechanism6.

Wilhelmy

Plate

7.

Electrobalance

8.

Barrier

9.

Barrier

Mechanism10.

Vibration

reduction

system

11.

Clean

room

enclosureLB仪器LB拉膜方法Langmuir-Schaefer方法等温Π－Α曲线0 100

200

300

400

500

600

700

800Area

per

molecule

A

(nm2)900 1000

1100

12000510液态15固态气态302520Surface

pressure

p

(mN/m)OutlineBasic

concepts生物体系中的自组装Tobacco

mosaic

virus

(TMV)DNA人工自组装分子自组装单层膜：烷基硫醇LB膜纳米晶体的自组装：金属纳米晶 辅助自组装（assistedself-assembly）模板辅助的自组装外场辅助的自组装：静电场，

交变电场，磁场自组装在纳米电子学中的应用单电子晶体管单分子器件结束语Gold

colloidal

particlesHAuCl4

+

Tannic

acid

+

Trisodium

citrateGold

nanocrystals8.3±8%nm单晶的单分散性好Jpn.

J.

Appl.

Phys.

40

(2001):

346–349Encapsulate

gold

nanocrystalsCH3SH3CSCH3SH3CSCH3SH3CSSSCH3SSSH3CSCH3SCH3SCH3SH3CSCH3SCH3CH3CH3SCH3SH3CS

SCH3SH3CH3CH3CSH3CSH3CAuMoleculecappedgold

nanoparticleSelf-assembly

of

gold

nanocrystalsEvaporation

of

the

solventformation

of

flows

in

the

solvent

whichtransport

the

particles

toward

the

surfaceThe

thickness

of

the

solutionbecomes

comparable

to

theparticle

sizethe

interactive

force

between

particlesinduced

by

the

surface

tension

of

the

solventcauses

the

particles

to

coalesce

into

close-packed

arraysJ.

Vac.

Sci.

Technol.

B

19

(2001):

115Set-up

for

the

self-assemblyNano

Letters,

4(2004):41Self-assembly

and

transferPreparation

of

PDMS

stampsStampingPatterned

nanoparticle

arraysPatterned

nanoparticle

arraySiO2/SiTuning

the

inter-particle

spacingC8C12C16100

nmx

100

nm100

nmx

100

nm100

nmx

100

nmSHSHSHOutlineBasic

concepts生物体系中的自组装Tobacco

mosaic

virus

(TMV)DNA人工自组装分子自组装单层膜：烷基硫醇LB膜纳米晶体的自组装：金属纳米晶

辅助自组装（assistedself-assembly）

模板辅助的自组装(TASA)外场辅助的自组装：静电场，交变电场，磁场自组装在纳米电子学中的应用单电子晶体管单分子器件结束语Principle

of

TASATASA过程中三种重要的力：FC：毛细作用力Fg：重力Fe：静电相互作用力J.

Am.

Chem.

Soc.,

123

(2001):8718Some

resultsPS球：2.5微米；孔：5微米

（直径）PS球：2.5微米；孔：6微米

（直径）Adv.

Funct.

Mater.,

13(2003):

907Attractive

vs.

repulsive

interactionThe

SEM

images

of

two

samples

that

were

obtained

through

the

TASA

process

from

PS

beadsterminated

in

the

-NH2

functional

group.

The

pH

value

of

the

colloidal

dispersion

was

(A)

6.5

and

(B)

8.5,

respectively.

The

strong

attraction

between

PS

colloids

and

template

surface

forsample

A

made

it

hard

to

move

the

particles

across

the

surface

using

capillary

force

alone.

As

aresult,

it

was

impossible

to

control

the

TASA

process

to

generate

aggregates

with

well-definedsizes

and

structures.

When

this

attractive

interaction

was

reduced

by

increasing

the

pH

value

ofthe

dispersion

medium,

one

could

obtain

well-defined

assemblies

through

the

TASA

process.The

irregular

shape

of

these

colloidal

particles

was

intrinsic

to

this

commercial

sample,not

caused

by

the

TASA

process.Control

over

the

single-layered

structuresSingle

layeredControl

over

the

double-layered

structuresDouble

layered(A)

The

SEM

image

of

an

arrays

of

tetrahedrons

that

were

assembled

from

1.0um

PS

beads

in

cylindricalholes

2um

in

diameter

and

2um

in

depth.

(b)

the

SEM

image

of

an

arrays

of

square

pyramidal

clustersassembled

from

1.0um

silica

colloids

in

pyramidal

cavities

(2.2um

wide

at

the

base)

(C)

zigzag

chains

of4.3μm

PS

beads

in

trenches

that

were

5

and

5.5

μm

in

width

and

depth,

respectively.

The

inset

in

part

Cshows

the

SEM

image

of

one

of

these

zigzag

chains

after

they

had

been

released

from

the

template

andredeposited

onto

a

silicon

substrate.Extension

to

smaller

scalesOutlineBasic

concepts生物体系中的自组装Tobacco

mosaic

virus

(TMV)DNA人工自组装分子自组装单层膜：烷基硫醇LB膜纳米晶体的自组装：金属纳米晶 辅助自组装（assistedself-assembly）模板辅助的自组装

外场辅助的自组装：静电场，

交变电场，磁场自组装在纳米电子学中的应用单电子晶体管单分子器件结束语Electrostatic

field

assisted

SANature

409(2001):

66InP

nanowireAC

field

assisted

SA:

DieletrophoresisTwo

different

particles

in

a

non-uniform

electric

field.

The

particle

on

the

leftis

more

polarisable

than

the

surrounding

medium

and

is

attracted

towardsthe

strong

field

at

the

pin

electrode,

whilst

the

particle

of

low

polarisability

onthe

right

is

directed

away

from

the

strong

field

region.DielectrophoresisAC

trapping

of

Au

NPsLaetitia

Bernard

Ph.D

thesisMagnetic

field

assisted

SAOptical

micrographs

of

Ni

nanowirechain

formation

after

precipitationfrom

a

water

suspension

in

externalmagnetic

fields

of

(a)

H<0.2

G,

(b)H=2

G,

and

(c)H=8

G.J.

Appl.

Phys.

91

(2002)

8549Magnetic

field

assisted

SA(a)

Plan-view

scanning

electron

micrograph

(SEM)

image

of

a

Pt–Ni–Pt

nanowire

trapped

by

elliptical

Nimagnetic

electrodes.

The

vertical

bars

are

Au

leads

for

electrical

measurements;

(b)

Close

up

SEM

imageof

the

trapped

nanowire,

with

the

substrate

tilted

70°.J.

Appl.

Phys.

91

(2002)

8549More:

Nano

Lett.

1(2001)

155OutlineBasic

concepts生物体系中的自组装Tobacco

mosaic

virus

(TMV)DNA人工自组装分子自组装单层膜：烷基硫醇LB膜纳米晶体的自组装：金属纳米晶 辅助自组装（assistedself-assembly）模板辅助的自组装外场辅助的自组装：静电场，

交变电场，磁场自组装在纳米电子学中的应用单电子晶体管单分子器件结束语Singleelectron

transistor

made

by

SA材料：10nm金纳米颗粒双功能分子：APTES，1，6-hexanedithiolJ.

Appl.

Phys.

82

(1997):

696Single

electron

transistor

made

by

using

SA96单电子隧穿导致的库仑阻塞J.

Appl.

Phys.

82

(1997):

6场效应效果OutlineBasic

concepts生物体系中的自组装Tobacco

mosaic

virus

(TMV)DNA人工自组装分子自组装单层膜：烷基硫醇LB膜纳米晶体的自组装：金属纳米晶 辅助自组装（assistedself-assembly）模板辅助的自组装外场辅助的自组装：静电场，

交变电场，磁场自组装在纳米电子学中的应用单电子晶体管单分子器件结束语Molecular

electronics分子尺度的新的物理现象，量子效应开始起主要作用实现用单个分子履行器件的功能的梦想分子尺寸很小：1-10nm；分子可以被设计和剪裁；分子可以是活性的/功能性的；化学合成的分子是全同的；很多分子有自组织功能。EemptyLUMO

=

lowestunoccupiedmolecular

orbitalHOMO

=

highestoccupiedmolecular

orbitalfullPhysics

today,

May

2003,

43Annu.

Rev.

Phys.

Chem.,2006,

57:

593Annu.

Rev.

Phys.

Chem.,2007,

58:

535Molecules

as

electrical

components?HSSHWires:conductingSpacers:insulatorsalkanesSwitchessmart

molecules:functionalityMechanical

SwitchGrunder

et

al.

JOCS

(2007)SSOOOptical

Switchvan

der

Molen

et

al.Nanotechn.

(2006)Molecular

Diode;Elbing

et

al.

PNAS

(2005)DiodesNNSOSOContactVATechniques

for

measuring

moleculesProc.

IEEE,

91,1785,

2003Mechanically

controllable

break

junction-

controllable

gap

size-

clean