Laser of Polymers

Adv Polym Sci (2004) 168: 51–246
DOI: 10.1007/b12682
Laser Application of Polymers

Thomas Lippert
Paul Scherrer Institut, 5232 Villigen-PSI, Switzerland
E-mail: Thomas.lippert@psi.ch
Abstract Laser ablation of polymers has been studied with designed materials to evaluate
the mechanism of ablation and the role of photochemically active groups on the ablation
process, and to test possible applications of laser ablation and designed polymers. The in-
corporation of photochemically active groups lowers the threshold of ablation and allows
high-quality structuring without contamination and modification of the remaining surface.
The decomposition of the active chromophore takes place during the excitation pulse of the
laser and gaseous products are ejected with supersonic velocity. Time-of-flight mass spec-
trometry reveals that a metastable species is among the products, suggesting that excited
electronic states are involved in the ablation process. Experiments with a reference material,
i.e., polyimide, for which a photothermal ablation mechanism has been suggested, exhibit-
ed pronounced differences. These results strongly suggest that, in case of designed polymers
which contain photochemically active groups, a photochemical part in the ablation mecha-
nism cannot be neglected. Various potential applications for laser ablation and the special
photopolymers were evaluated and it became clear that the potential of laser ablation and
specially designed material is in the field of microstructuring. Laser ablation can be used to
fabricate three-dimensional elements, e.g., microoptical elements.
Keywords Laser ablation · Ablation mechanism · Photopolymers · Polyimide · Spectroscopy
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
1.1 Laser Ablation History . . . . . . . . . . . . . . . . . . . . . . . . . . 53
1.2 Laser Ablation of Polymers. . . . . . . . . . . . . . . . . . . . . . . . 56
1.2.1 Mechanisms of Ablation . . . . . . . . . . . . . . . . . . . . . . . . . 58
1.2.2 Why Special Polymers? . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2 Ablation Mechanisms of Novel Photopolymers . . . . . . . . . . 62
2.1 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
2.2 Ablation Characteristics–Mechanism of Ablation . . . . . . . . . 65
2.2.1 Etch Rates and Qualities . . . . . . . . . . . . . . . . . . . . . . . . . 65
2.2.1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
2.2.1.2 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
2.2.1.3 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
2.2.1.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.2.2 Analysis after Irradiation . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.2.2.1 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2.2.2.2 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
2.2.2.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
2.2.3 Nanosecond Transmission Studies . . . . . . . . . . . . . . . . . . . 98
2.2.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
Springer-Verlag Berlin Heidelberg 2004

52 Thomas Lippert
2.2.3.2 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . 100

2.2.3.3 Application of the Model . . . . . . . . . . . . . . . . . . . . . . . . . 108
2.2.3.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
2.2.4 Nanosecond Interferometry . . . . . . . . . . . . . . . . . . . . . . . 113
2.2.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
2.2.4.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
2.2.5 Nanosecond Shadowgraphy . . . . . . . . . . . . . . . . . . . . . . . 122
2.2.5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
2.2.5.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2.2.5.3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
2.2.5.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
2.2.6 Time-of-Flight Mass Spectrometry (TOF-MS). . . . . . . . . . . . 131
2.2.6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
2.2.6.2 Experiment and Curve Fitting . . . . . . . . . . . . . . . . . . . . . . 132
2.2.6.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
2.2.6.5 Additional Time-of-Flight Mass Spectrometry Experiments. . . 143
2.2.7 Excimer Lamp Irradiation . . . . . . . . . . . . . . . . . . . . . . . . 146
2.2.7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
2.2.7.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
2.2.8 Picosecond Infrared Spectroscopy . . . . . . . . . . . . . . . . . . . 150
2.2.8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
2.2.8.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
2.2.8.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
2.3 Comparison with a Reference Polymer (Polyimide) . . . . . . . . 159
2.3.1 DRIFT Analysis of Polyimide After UV Laser Irradiation . . . . 159
2.3.1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
2.3.1.2 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
2.3.1.3 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
2.3.1.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
2.3.2 DRIFT of Kapton After Thermal Decomposition . . . . . . . . . . 174
2.3.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
2.3.2.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
2.3.2.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
2.4 Discussion of the Ablation Mechanisms . . . . . . . . . . . . . . . 189
2.4.1 Designed Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
2.4.1.1 Polyimide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
2.4.1.2 Additional Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . 192
2.4.1.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3.1 Laser Ablation Resists (Dry Etching) . . . . . . . . . . . . . . . . . 199
3.1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
3.1.2 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201

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Adv Polym Sci (2004) 168: 51–246

Laser Application of Polymers

Keywords Laser ablation · Ablation mechanism · Photopolymers · Polyimide · Spectroscopy

Springer-Verlag Berlin Heidelberg 2004

2.2.3.2 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . 100

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