Second Harmonic Generation (SHG)

GVHD: L Th Qunh Anh

HV:

Trnh Th Qunh Nh
L Duy Nht

NI DUNG
1. Gii thiu v sng hi bc hai
Sng hi bc 2
Nguyn tc
Lch s

2. ng dng
Laser mu
Knh hin vi SHG
Hiu ng b mt

Sng hi bc 2 (SHG)
SHG (hay cn gi l s nhn i tn s) l qu
trnh phi tuyn, trong nhng photon tng tc vi
vt liu phi tuyn, kt qu l to ra nhng photon mi
c nng lng gp i (do tn s gp i v bc
sng gim mt na so vi photon ban u).
y l mt trng hp ca s pht tn s tng.
SHG

SHG

Sng hi bc 2 (SHG)

P = e0 c(1)E + e0 c(2)EE + e0 c(3)EEE +

P: phn cc ca mi trng
e0: hng s in mi trong chn khng
E: cng in trng
c(i): hng s

D = e0E + P = eE
Trong quang phi tuyn: n2 = 1 + c(1)

Sng hi bc 2 (SHG)
S dng bc sng = 0 th nh
sng ra s c bc sng = 0/2
Tn s nhn i = 20

Energy is
conserved

Cng in trng tng

hp:

E Elight Re[ E0 exp(i0 t )]

PNL c ( 2 ) E 2 ~ c ( 2 ) Re[ E02 exp( i 20 t )]
Rigorous solution:

E1 E10 U1 ( x, y) exp(ik1 z 1 t )
E2 E20 U2 ( x, y) exp(ik2 z 2 t )

2 21

2 E
2
E 0e 0 2 0 2 PNL
t
t
2

D DijkU 2iU1 jU1k

ijk

d
E1 i1 0 DE2 E1* exp[i(2k1 k 2 ) z ]
dz
e1

0 1
d
E2 i2
DE12 exp[i(2k1 k 2 ) z ]
dz
e1 2

iu kin hp pha

Ch khi 2k1 = k2 th c hiu ng SHG

~ 100% hiu ng SHG c

th xy ra nu c s
ng b v pha

2k1 = k2

2k1 k2

Lch s pht trin

** Nm 1961, vi s ra i ca tia laser, P.A.Frankin, A.E. Hill,
C.W.Peters v G. Weinreich (i hc Michigan, Ann Arbor) pht hin ra
hin tng pht sng hi bc 2.
Water

Fundamental
Laser Light
694nm

Quartz

Second
Harmonic
Generation
(SHG)
347nm

P. A. Frankin

** Leslie Loew v Paul Pampagnola (trng i hc Connecticut) ng

dng SHG thu nh ca phn t.
** Joshua Salafsky i tin phong vic s dng k thut trong vic nghin
cu phn t sinh hc bng vic nh du chng vi th hot ng SH

NG DNG

Khoa hc vt liu
Sinh hc
Tm kim tinh th photonic c ngun
gc t vt liu sinh hc
nh ca cc m

Hiu ng b mt

Khoa hc vt liu
Tnh cht ca vt liu GaN
Vi Laser Cr:Foxterite1230
SHG 615-nm
Trng p in tng
Khng cng hng.

B tr th nghim

C th s dng bung
cng hng tng
hiu ng SHG.

KNH HIN VI
Knh hin vi:
tng phn
phn gii
xuyn su
Tnh khng xm nhp

KNH HIN VI CI TIN

Knh hin vi trng ti
Knh hin vi DIC hay PC

Knh hin vi hunh quang

Knh hin vi hi t
Knh hin vi sng hi

KNH HIN VI
Hunh quang nhiu photon

S pht sng hi

u l qu trnh phi tuyn

Xuyn su cao vi bc sng IR
L knh hin vi khng kt hp
Lm phai mu nh
Lm hng nh
Bin mu
Ph thuc mnh vo bc sng

L knh hin vi kt hp
Khng mt mt nng lng/Khng hp thu/ lm
phai mu nh
khng lm hng nh
Ni sinh (Khng bin mu)
S chn bc sng km

KNH HIN VI SHG (SHG microscopy)

V hnh

suy gim thp nht bc sng

khong 1200 n 1300 nm
Xuyn su trong mu sinh vt
C tc dng trong vng nh sng kh kin
Gim hunh quang
Khng lm hng nh
Thch hp vi cht x, si
Khng nhy vi u thu silic

B ln

KNH HIN VI SHG (SHG microscopy)

ng dng trong sinh hc

Tinh th photonic t vt liu sinh hc

S phn bo b phi c nga

SHG:
Tinh th ha dy vi cu trc hnh ng
Thu nh sau khi vi cu trc hnh ng phn tn.

SHG ca tinh bt

SHG trong si gn

SHG t protein, khng phi t m

KT LUN (KNH HIN VI SHG)

tng phn tng ln ng k
phn gii: 400nm
xuyn su >1.5mm
Tnh khng xm nhp
Quan st c thi k phi ko di
V nn cc tnh cht ca vt liu
Th hin in trng 3 chiu
Tm kim tinh th photonic c ngun gc sinh hc
Pht trin ngnh sinh vt hc

(SHG rt nhy vi cu trc phn t)

Nghin cu mng mng
ng lc hc
Hin th cng in trng
u d hiu ng nhit
nh su bn trong ca m

S hp th ca ion thiocyanate lp phn cch

dodecanol/nc bng UV SHG
1. C s l thuyt:
1.1 Gii thiu chung
1.2 Hp ph v kiu hp ph Langmuir
1.3 Cu trc Dodecanol/nc
2. Kt qu v tho lun
Ph hp th UV ca NaSCN
Ph cng SHG theo nng
Ph cng SHG theo nng NaSCN
Ph cng SHG theo nng KSCN
3. Kt lun:

1.1 Gii thiu chung

Nhng kt qu thc nghim v l thuyt gn y chng minh
xp cht ca phn t c thit lp do s sp xp c c ca cc ion
ti b mt. S lin kt ca ion b mt l qu trnh kt hp phc tp ca
cc phn t (complex molecules). Hin tng pht sng hi bc 2 cng
hng t ngoi (resonant UV second harmonic generation) l do cc ion
thiocyanate (SCN- ) dao ng mnh (strongly chaotropic) hp ph lp b
mt gia nc v lp n dodecanol.
Nng lng t do ca hp ph Gibbs (Gibbs free energy of
adsorption) c xc nh l 6.7 1.1 kJ/mol (NaSCN) and 6.3 1.8
kJ/mol (KSCN). S trng hp v gi tr trn quyt nh (determined) l do
tnh cht ca thiocyanate (SCN- ) b mt gia khng kh v nc.
Nu nng 4M th tn hiu SHG cng hng s tng gin on,
chng t rng c s thay i cu trc mt vng b mt.
i lc in t ca cc ion khc nhau lp b mt c Chen
nghin cu bng cch dng ph dao ng tn s tng (vibrational sum
frequency spectroscopy (VSFS))

1.2 Hp ph v kiu hp ph Langmuir

Hp ph l qu trnh t tp (cht cha, thu ht) cc phn
t kh, hi hoc cc phn t, ion ca cht tan ln b mt phn chia
pha. B mt phn chia pha c th l lng rn, kh lng, kh rn.
Cht m trn b mt ca n c s hp ph xy ra gi l cht hp
ph, cn cht m c t tp trn b mt phn chia pha c gi l
cht b hp ph.
Trong qu trnh hp ph, nng lng t do b mt ca h
gim, ngha l G < 0. ng thi hn n ca h gim (do cc
tiu phn ca cc cht b hp ph trn b mt cht hp ph c
sp xp mt cch c trt t) ngha l S < 0. Do t phng trnh
nng lng ca cng thc GIBBS (Th ng p ng tch).
G = H T.S < 0.
T suy ra: H < 0.
Ngha l qu trnh hp ph l qu trnh ta nhit. iu ny hon
ton ph hp vi thc nghim. Hiu ng nhit ca qu trnh hp
ph c gi l nhit hp ph.

1.2 Hp ph v kiu hp ph Langmuir

Hp ph vt l: Cc nguyn t b hp ph lin kt vi nhng tiu
phn (nguyn t, phn t, cc ion) b mt phn chia pha bi lc lin
kt vander walls yu.
Ni mt cch khc, trong hp ph vt l cc phn t ca cht b hp ph v
cht hp ph khng to thnh hp cht ha hc (khng hnh thnh cc lin
kt ha hc) m ch b ngng t trn b mt phn chia pha v b gi li trn
b mt bng lc lin kt phn t yu(lc vander walls) v lin kt hiro. S
hp ph vt l lun lun thun nghch. Nhit hp ph khng ln.
Hp ph ha hc: C nhng lc ha tr mnh (do cc lin kt
bn ca lin kt ion, lin kt cng ha tr, lin kt phi tr) lin kt nhng
phn t hp ph v nhng phn t b hp ph to thnh nhng hp cht
ha hc trn b mt phn chia pha.
Ni mt cch khc hp ph ha hc xy ra khi cc phn t hp ph to
hp cht ha hc vi cc phn t b hp ph v hnh thnh trn b mt
phn chia pha (b mt pha hp ph). Lc hp ph ha hc khi l lc
lin kt ha hc thng thng (lin kt ion, lin kt cng ha tr, lin kt
phi tr) s hp ph ha hc lun lun bt thun nghch.

1.2 Hp ph v kiu hp ph Langmuir

Hp ph ng nhit ca Langmuir:
Trong qu trnh hp ph nhng phn t kh b hp ph s
li trn b mt ht xc tc trong mt thi gian nht nh
tip nhn nng lng v thc hin qu trnh nh hp ph. Qu
trnh hp ph v qu trnh nh hp ph xy ra ng thi cho n
khi ht phn ng t c trng thi cn bng.
thit lp c phng trnh ng hc cho qu trnh hp ph,
Langmuir a ra mt s iu kin sau (thuyt hp ph ng
nhit ca Langmuir):
Tt c cc tm hot ha u c tnh cht nh nhau.
S tm hot ha khng thay i theo thi gian.
Mi tm hot ha ch c th hp ph mt phn t b hp
ph.
Gia cc phn t b hp ph khng c tc ng qua li.

1.2 Hp ph v kiu hp ph Langmuir

Lc hap phu - Adsorptive Forces

1.3 Cu trc Dodecanol/nc

Dodelcanol l mt hydro cacbon no c nhm chc ca ru (OH-).
Cu trc ni ti ca Dodecanol/nc l mt chui di lin kt ca
dodecanol v nc lp phn cch ca 2 cht. Din tch b mt ca
phn t dodecanol -1 trn b mt nc l 20 Angron2. Dng ph tia X
ngi ta khng nh dodecanol nm dc (thng ng) so vi b mt
nc. Do gc OH- ca dodecanol c th lin kt vi nguyn t H
ca nc.

Dodecanol -1 c trong cht bo (alipphatic chain). V vy m

ngi ta s dng ph dao ng tn s tng (VSFS - vibrational sum
frequency spectroscopy) xc nh r ch hng (khuyt tt) ca cc
cht bo nh vo s chuyn i pha 2D theo nhit (Tm(2D))
S hp th b mt ca thiocyanate ti b mt
thiocyanate/nc khng lm gin on mt ca thiocyanate v
tnh nh hng ca lp n dodecanol.

Ph hp th UV ca NaSCN

UV absorption spectrum of aqueous

sodium thiocyanate.
(Ph hp th UV ca NaSCN)

Ph cng SHG theo nng

Cng SHG ph thuc vo
bn cht ca lp n
dodecanol/nc.
Cng SHG tng ln r nt
khi nng ion tng.

SHG response for NaSCN and KSCN solutions

plotted as a function of bulk concentration

Ph cng SHG theo nng NaSCN, KSCN

SHG response for NaSCN (A)

and KSCN (B) solutions and the
corresponding Langmuir fits

Kt lun:

S hp th ion m b mt ca lp n ca chui ru v nc, s

dng cng hng SHG do s hn n (hn lon) mnh ca ion
thiocyanate. Php phn tch Langmuir ch ra rng s biu hin ca ion
thiocyanate ph thuc vo nng th tch. Cc ion dng ng nht c
hiu ng i lc nh ln cc ion thiocyanate b mt. Kt qu tm ra
b mt nc/cht bo, v d t s hp th ca ion thiocyanate ngi ta
hy vng c th hp th nhiu OH thnh t bo.
nng cao, cng SHG tng mt cch gin on.
nng thp cho thy c s thay i trong cu trc b mt. Php phn
tch vi nng cao c lin quan n ngnh sinh l hc.

Ti liu tham kho:

1. Gio trnh Quang phi tuyn _Trn Tun_NXB HQG Tp HCM

2. Hiu ng quang hc phi tuyn_ Trn Tun_L Vn Hiu_ NXB HQG Tp

HCM
3. www.pnas.org/cdi/doi/10.1073/pnas.0904800106
4. Adsorption of thiocyanate ions to the dodecanol/water interface
characterized by UV second harmonic generation - Robert M. Onoratoa,
Dale E. Ottena, and Richard J. Saykallya,b,1 - Department of Chemistry,
University of California, Berkeley, CA 94720; and bChemical Sciences
Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94618
Cc bi vit khc