MID-IR Ultrafast Spectroscopy DNQ

Photodecomposition of Diazonaphtoquinone (DNQ) by

Wolff rearrangement

Full name: 2-diazo-1-naphthol-5-sulfonic acid (DNQ)

DNQ is the photoreactive compound of photoresist materials used in

photolitography for production of integrated circuits.

The Wolff rearrangement is a rearrangement reaction converting a -

diazo-ketone into a ketene:

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MID-IR Ultrafast Spectroscopy DNQ

Motivation:

1. To clarify the mechanism of Wollf rearangament on ultrashort time scale

2. To achieve VMP in liquids

2
MID-IR Ultrafast Spectroscopy DNQ

? Carbene

Ketene Enol
DNQ

Short time dynamics

The mechanism of Ketene formation is
long under discussion. Concerted
reaction or stepwise reaction with
Carbene as intermediate
indenecarboxylic ester
J. Andraos et al. J.Am. Chem. Soc. 115 10605 (1993)
J. J. M.Vleggaar et al J. Am. Chem. Soc. 116 11754 (1994)
D. Wolpert et al. Chem. Phys. 129 094504 (2008)
Q. Li et al J. Phys. Chem. Lett. 3 1056 (2012) 3
 MID-IR Ultrafast Spectroscopy DNQ

4.0

3.5
After 20 min UV
DNQ in Methanol 100m Before
3.0
13 mmol/L 15

2.5
DNQ
Absorption

Absorption
2.0
10
1.5
1708
Indene C. Ester
1.0

0.5 5
Methanol
0.0
200 250 300 350 400 450 500
Lambda(nm)
0
UV/VIS spectrum of DNQ in methanol
1200 1400 1600 1800 2000 2200
-1
Wavenumber (cm )

MID-IR of DNQ in methanol before and after UV exposure

Calculation of MID-IR spectrum of intermediate species

D. Wolpert et al. J. Chem. Phys. 129, 094504 (2008,)
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MID-IR Ultrafast Spectroscopy DNQ

Vibrational modes of both Ketene and DNQ fall into the same interval
covered by MID-IR fs laser spectrum
DNQ KETENE

C=N=N Stretching:
C=C=O Stretching:
2084 cm-1
2118 cm-1 2128 cm-1
2168 cm-1

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MID-IR Ultrafast Spectroscopy DNQ

Model surface for the dynamics:

Q1 (CN dissociation coordinate)

Q2 (ring rearrangement coordinate) Q. Li, A. Migani and L.Blancafort,
J. Phys. Chem. Lett. 2012, 3, 10561061 6
MID-IR Ultrafast Spectroscopy DNQ

Transient Absorption
Photodiode Array
MID-IR Probe

UV Pump

MID-IR Pump

White light Probe

Multichannel
MID-IR Detector

1. MID-IRPump, MID-IR Probe

Vibrationaly 2. UV Pump, MID-IR Probe
Mediated 3. UV Pump, MID-IR Pump, MID-IR Probe
Photodissociation 4. UV Pump, WL Probe
(VMP) 5. UV Pump, MID-IR Pump, WL Probe

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MID-IR Ultrafast Spectroscopy DNQ

An earlier attepmt of VMP in liquid, trans to cis isomerisation of stilbene...

...did not show

influence of
vibrational
preexcitation on the
photoisomerisation

The Influence of Vibrational Excitation on the Photoisomerization

F.Fleming Crimet al J. Phys. Chem. A, 114 9788 (2010) 8

MID-IR Ultrafast Spectroscopy DNQ

UV MID-IR
Dynamics of photoproduct Ketene
With quantum yield Q
N1 (t ) QN EXC e t /t1 S1
N 2 (t ) QN EXC e t /t1 C e t /t1 e t /t 2
Very fast
N 3 (t ) QN EXC e t /t1 De t /t1 Ce t /t 2 1
Dynamics of the bleach recovery - DNQ
Q
t /t 0
DNQ(t ) A Be N1(t)
t1
1-Q N2(t)
t2
S0 t0 N3(t)
DNQ(t)

DNQ Ketene

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MID-IR Ultrafast Spectroscopy DNQ

Transient Absorption, UV pump, MID-IR probe

DNQ ground state beleach

Ketene formation

Ground state bleach removing, pure Ketene signal

Shift to the blue in time vibrational cooling

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MID-IR Ultrafast Spectroscopy DNQ

MID-R pumpUV pump, MID-IR probe

(towards VMP)

DNQ ground state beleach

Ketene formation

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MID-IR Ultrafast Spectroscopy DNQ

Ketene formation DNQ bleach

4,0
1,0
2,0

0,0

-2,0 UV pump 0,0

-4,0
Abs.(mOD)

t0=9.8.2 ps

Abs.(mOD)
-6,0
-1,0
-8,0

-10,0
A=0.69 mOD
-12,0
B=0.68 mOD -2,0
-14,0

-16,0
-20 -10 0 10 20 30 -3,0
t(ps) -20 -10 0 10 20 30
t(ps)

4,0 1,0

2,0

0,0
0,0
-2,0 UV & MID-IR Pump
-4,0
Abs.(mOD)

Abs.(mOD)
-6,0 -1,0

-8,0
t0=3.8.2 ps
-10,0 A=1.37 mOD -2,0
-12,0
B=1.41 mOD
-14,0

-16,0 -3,0
-20 -10 0 10 20 30 -20 -10 0 10 20 30
t(ps) t(ps)
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MID-IR Ultrafast Spectroscopy DNQ

Introduction of MID IR pump changes the short time dynamics of the DNQ
bleach but does not change the final yield of photoproduced Ketene

That means that the 2128 stretching mode is not the reactive coordinate
Reactive coordinate must be in FC region.

Next step for achieving VMP is to try with 1600 mode, ring-rearrangement
mode

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MID-IR Ultrafast Spectroscopy DNQ

...but in WL transient absorption new intermediate is found (Carbene?)

UV pump (400nm) & MID-IR pump (2100 cm-1), WL absorption.

Short lived bands appear at 340 nm and 440 nm

30

Shift to the blue at later time

delays indicates vibrational
20
cooling.
Time Delay (ps)

10

300 350 400 450 500

Wavelength (nm)

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MID-IR Ultrafast Spectroscopy DNQ

Ketene formation follows almost immediately after UV pulse excitation.

That supports concerted reaction.

An intermediate is observed with WL TA which lasts about 7 ps. Only

in VMP type of experiments.

Next candidate for VMP is 1600 ring-rearrangement mode.

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