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第 5 章 固体的光性质和光功能材料 PowerPoint PPT Presentation


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第 5 章 固体的光性质和光功能材料. 固体的光性质,从本质上讲,就是固体和电磁波的相互作用,这涉及晶体对光辐射的反射和吸收,晶体在光作用下的发光,光在晶体中的传播和作用以及光电作用、光磁作用等。基于这些性质,可以开发出光学晶体材料、光电材料、发光材料、激光材料以及各种光功能转化材料等。在本章中,我们从固体对光的吸收的本质开始,然后介绍光电材料、发光材料和激光材料以及分子荧光材料等。. 导带. 能隙 (禁带). 价带. §5.1 固体对光的吸收与光电转换材料 5 . 1 . 1 固体光吸收的本质. 1. 纯净物质对光的吸收 基础吸收 或 固有吸收

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第 5 章 固体的光性质和光功能材料

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5

5


5


5

5.1

511

1.

5.1


5

~25m250nm0.05~5evCaF2200nm(6ev)NaCl8evAl2O39ev


5

(

-excition5.2-~1m


5

2.

5.3

CV

EVKT


5

DVEgEDGaAsEg1.1592evED0.006evDV1.5132ev1.5132evDVDDV


5

CAEgEAGaAsEA0.03evCA1.49evGaAs1.49ev-CDA


5

DA DA.

Eb= - e2/4Kr 1.1

Eg-ED-EA-Eb


5

5.1.2

Eg

Eg = h= hc/ 1.2

= hc/ Eg 1.3

h6.6310-34 Jsc


5

-Eg

Al2O3Al3+O2-Al3+O2-9ev


5

0.1%Cr3+1%Cr3+Cr3+Al2O3

-7.4


5

7.4


5

5.1.3

1.

1ev


5

2.

5.3npnpp-np-nnpp-nnpp-n5.5p-n


5

GaAs1-xPxxp-nPnnpPnnCdSpCu2Sp-n

ap-n bp-n

5.5 p-n


5

3.

5.6:abc

5.6


5

5.7AgBr

7.7 AgBr-185546nm6.51010/

7.7 AgBr


5

CdSPbSPbSePbTe


5

5.2

5.2.1

1

Luminescence

Photoluminescence

Electroluminescence

Cathodoluminescence


5

2

7.8ZnS:Cu 7.91Zn2SiO4Mn2

7.8

7.9


5

I

1/2

1/27.10

3

~100nmCaWO4

~50nmSr(PO4)2ClEu3+

~0.1nmGdVO4)Eu3+Eu2+3

7.10


5

3

NN

B = N / N 2.1

B = E / E 2.2

E=h

B = E / E= h / h= / 2.3

B = / 2.4


5

Fluorescence<10-8

Phosphorescence

J0J010%

<1s 1~10s

10-2~1ms 1~100ms

0.1~1s >1s


5

3323xyzxyzQ

Q= ax+by+cz 2.5

3

x= y= z= 2.6

x+y+z=1xyz

7.11xy


5

7.11


5

722

1

ZnSCaWO4Zn2SiO4Mn2+Sn2+Pb2+Eu2+Activators2Sensitizer5.12hh>Stokes shift

(a) (b)

7.12


5

2.

Configurational Coordinate Model CCM

0.01cm-1- Franke-Condon


5

Configration5.13re012

7.13


5

:

5.14AB

-ABCCADEAB>ECAECD

7.14


5

:

Thermalquenching effect5.14

7.14EEESpillorer PointEEE

7.14


5

re

nonrediative transition.

nonrediative energy transition5.15

a

b


5

Fe3+Co2+Ni2+

5.15


5

3. nati-stokes

YF3NaLa(WO4)2- NaYF4Yb3+Eu3+2

7.16(a)

7.16(b) 2


5

(a) (b)

5.16

2


5

Hg

185nm

254nm

5.17

4.

5.17254185nm


5

(1) Cd2B2O5Zn2SiO43Ca(PO4)2Ca(Cl,F)2

(2) ZnSAg+Sb3+Eu2+ZnS5.17

Ag+ 4d10 4d95p

Sb3+ 4d105s2 4d105s5p

Eu2+ 4f7 4f65d

7.17


5

Sb3+Eu2+Ca5(PO4)3FSb3+Mn2+5.1

5.1

Zn2SiO4 Mn

Y2O3 Eu

CaMg(SiO3)2 Tl

CaSiO3 Pb, Mn

(Sr,Zn)(PO4)2 Sn

Ca(PO4)2Ca(Cl,F)2 Sn,Mn


5

170 -20.2Acm-240s0.6~0.8

(1)

ZnSCdS:Ag,AuZnSCdS:P,As

y7 Zn,CdS:Ag 560nm

y8 ZnS:Ag 453nm

y26 y7+y8 455nm,558nm

:

Zn,Be2SiO4:MnCa,MgSiO3:Ti


5

2

5.115.2

YVO4EuY2O3:Eu Y2O3S:Eu3Tb3+Ho3+Er3+YVO4ErYVO4HoYVO4TbY2O3S:Eu,TbZnS:AgYVO4TmZnS:AgEu2+Sr3(PO4)2:Eu


5

5.2

nm%10%

x y

Zn3(PO4)2:Mn 0.665 0.335 663 6.7 27ms

Zn,CdS:Ag 0.665 0.336 670 16.0

YVO4Eu 0.664 0.330 620 7.1 1-3ms

Y2O3:Eu 0.640 0.352 610 8.7 1-3ms

Y2O3S:Eu 0.648 0.344 626 13.0 0.5-2ms

Zn2SiO4:Mn 0.218 0.712 525 7.4 25ms

Zn,CdS:Ag 0.300 0.600 535 19.8 0.05-2ms

Zn,CdS:Al 0.357 0.596 535 18.4 15-30s

ZnS:Cu,Al 0.243 0.633 530 21.8 15-30s

ZnS:Cu,Au,Al 0.332 0.602 535 15-30s

ZnS:,Ag 0.146 0.057 450 20.4 5-15s


5

7.2.3

LaserLight amplification by stimulated emission of radiation3

1

216Kr

3


5

1.

Ruby lasserMaiman 19600.05%wt Cr3+5.19Cr3+5.20


5

103cm-1

4F1

20 4F2

10 2E

693.3nm

0 4A2

7.19 Cr3+

7.19Cr3+d4A24F14F22E2E510-32E693nm


5

7.20

5.201-21Q1

Nd3+YAG5.20Nd3+4F3/2~10-4Nd/1060nmNd/ YAG1064nm


5

3

1CaF2BaF2HgF2Nd3+Sm3+Dy3+U3+

2CaF2-YF3LiYF4Gd3+Tb3+

3Al2O3: Cr3+LiNbO3: Nd3+MgO:Ni2+YAG

4NdP5O14Nd3+5041021cm-3YAG: Nd3+~1.2%60

5LiF: Nd3+LiF: Na+

6Ca5(PO4)3F: Nd3+Sr5(PO4)3F: Nd3+La2O2S: Nd3+


5

7.2.4

electroluminescenceEL

1.

/

/7.21S0S1S1S0T1S0


5

7.21 /


5

ITO

ITO

a

b

/organic light emitting diodeOLED//7.22

In-SnITOAlGaMgITO7.22a

7.22b


5

ITO

ITO

c

d

7.22c

7.22d

Ca L i/Al Mg/Ag Mg Mg/Al Al Ag ITO

/eV 2.9 3.2 3.6 3.7 3.7 4.3 4.4 4.7


5

OLED/31

OLED


5

2. /

a. KodakTangDVM7.23Allq3OLEDCT-CTAllq3TPD


5

7.23 DCM


5

bPBDOLED

TgHOMOLUMOHOMOLUMO7.25PBD


5

7.25PBD


5

NPAMLIDA4208000cd/m2


5

c. oligo phenylenevinylenes OPVOPVOPVOPVDO5TTPA3T13000cd/m27.26OPV


5

OLEDMn+123


5

AlAlq3Al8-Alq3530nmC-5C-4C-2C-4506nmC-2C-3470nmNCC-5440nmC-4580nm


5

AlOLEDSchiffBeBq2ELAlq3516nm19600cd/cm2EL

254f100EL


5

Eu35D07F2617nm4nmOLEDEu3-TTADNMPhen

Tb35D47F5545nm10nmEu3-acacPhen7.27 7.28


5

S1

T2

T1

S0

7.27


5

7.28


5

poly phenphylenenPPVPLED


5

PPVPPVPPVMEH-PPV590nmBMOS-PPVLUMOCN-PPVPPPPPPPT3-7.29


5

7.29


5

PLPTPPPPPV7.3-


5

OLEDAlq37.31Eu


5

2525

1:3OLED25575


5

metal-to-ligant charge transport ,MLCTFoesterDexter

FoesterDonor(D)-Accept(A)-dipole-interaction--

DexterD-Aelectron exchange

FoesterDexterD-A--FoesterFoester-FoesterDexter


5

OLEDPtIrOsRuAuCu7.32

PtOEPAlq3ELPtOEP580nm650nmEQE4Dexter620Alq31Alq3DexterAlq31FoesterIr(PPy)3EQE7.5PtOEPIr(DBQ)3(acac)610612nm73870cd/cm2EQE12.4


5

7.32


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