Xin
Liu
ab,
Stephan
Prinz†
a,
Heino
Besser
cd,
Wilhelm
Pfleging
cd,
Markus
Wissmann
bd,
Christoph
Vannahme‡
ba,
Markus
Guttmann
bd,
Timo
Mappes§
b,
Sebastian
Koeber
be,
Christian
Koos
be and
Uli
Lemmer
*ab
aLight Technology Institute (LTI), Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany. E-mail: uli.lemmer@kit.edu
bInstitute of Microstructure Technology (IMT), Karlsruhe Institute of Technology, 76344 Eggenstein-Leopoldshafen, Germany
cInstitute for Applied Materials - Applied Materials Physics (IAM-AWP), Karlsruhe Institute of Technology, 76344 Eggenstein-Leopoldshafen, Germany
dKarlsruhe Nano Micro Facility, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
eInstitute of Photonics and Quantum Electronics (IPQ), Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany
First published on 7th August 2014
The integration of organic semiconductor distributed feedback (DFB) laser sources into all-polymer chips is promising for biomedical or chemical analysis. However, the fabrication of DFB corrugations is often expensive and time-consuming. Here, we apply the method of laser-assisted replication using a near-infrared diode laser beam to efficiently fabricate inexpensive poly(methyl methacrylate) (PMMA) chips with spatially localized organic DFB laser pixels. This time-saving fabrication process enables a pre-defined positioning of nanoscale corrugations on the chip and a simultaneous generation of nanoscale gratings for organic edge-emitting laser pixels next to microscale waveguide structures. A single chip of size 30 mm × 30 mm can be processed within 5 min. Laser-assisted replication allows for the subsequent addition of further nanostructures without a negative impact on the existing photonic components. The minimum replication area can be defined as being as small as the diode laser beam focus spot size. To complete the fabrication process, we encapsulate the chip in PMMA using laser transmission welding.
In terms of the gain materials, small molecules such as tris(8-hydroxyquinoline) aluminum (Alq3) doped with the laser dye 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) compete with conjugated polymers. The former class of materials can be evaporated locally using shadow masking, and can thus be combined with pre-defined grating structures. On the other hand, conjugated polymers can be processed by inexpensive solution-based techniques such as spin coating, dip-coating and doctor blading. These methods, however, result in an organic semiconductor layer covering the whole substrate. Lateral control can be achieved using printing techniques. A particularly interesting approach is the use of ink-jet printing. Ink-jet printing has already been successfully applied to the fabrication of various organic electronic devices, such as organic transistors,15,16 organic solar cells17,18 and organic light-emitting diodes.19,20 We have recently successfully fabricated organic semiconductor distributed feedback laser pixels by ink-jet printing the active layer from a conjugated polymer solution. Utilizing an optimized mixture of high-boiling and low-boiling solvents for dissolving the polymer, the ink-jet-printed film profile is optimized, thus creating uniformly emitting organic lasers. Such devices show lasing thresholds as low as 76 nJ per pulse and a spectrally homogeneous laser emission over large areas.21
The laterally controlled fabrication of DFB gratings for organic semiconductor lasers has only been addressed so far by using nanograting transfer to transfer the gratings onto a homogeneous gain material layer,22 and a rather complex approach using direct electron beam lithography (EBL) on conjugated polymers.23 On the other hand, various substrate scale techniques such as laser interference lithography (LIL)24 and nanoimprint lithography (NIL)25 are available to achieve the low-cost fabrication of high-quality DFB corrugation nanostructures on an LOC platform. Among them, NIL promises the mass-production of extremely fine structures with feature sizes down to 10 nm.26 The resolution of NIL can be further improved by the fabrication of a rigid mold with sub-10 nm features.25 Nowadays, two main subjects of NIL are frequently used in the fabrication of DFB corrugations for organic semiconductor laser applications: thermal nanoimprint lithography (TNIL, also known as hot embossing) and UV-assisted nanoimprint lithography (UV-NIL).27–30 UV-NIL is an option to fabricate localized DFB corrugations without negative effects on the existing structures, but it is mandatory to use special photoactive materials in the process. This limitation results in a narrow application field in the fabrication of LOC systems. TNIL is advantageous for parallel replication of all structures from a master stamp onto a common polymer substrate. Nevertheless, it has three major drawbacks. First is the difficulty in the fabrication of pre-defined partial structures from a rigid master stamp with structures for different purposes. Secondly, the large-area heating can be detrimental for existing LOC passive photonic elements and microfluidic channels. The third issue is the long heating and cooling time.
These limitations of TNIL can be overcome using a near-infrared high-power diode laser beam.31,32 In this work, we demonstrate a novel laser-assisted replication to fabricate localized surface-emitting (2nd order) and edge-emitting (1st order) organic distributed DFB laser pixels on a poly(methyl methacrylate) (PMMA) substrate. Our technique allows for fast replication with standard TNIL materials due to the localized heating. Not only is the process time reduced, the localized heating also provides the unique benefit to replicate only parts of the existing structures on a master stamp. Additionally, since only the defined areas are to be heated, it allows for subsequent additive fabrication of DFB corrugations while all the other areas are retained. The minimum localized replication area and the influence of the process parameters on corrugation quality are investigated. A functional LOC is finished after encapsulation via laser transmission welding, protecting the device from air and water.33–35
To perform the experiments, a high-power diode laser system (Fisba Optik, FLS Iron High Power Diode) with an emission wavelength of 940 nm and a maximal power of 50 W is used. As shown in Fig. 1(b), the diode laser and a pyrometer, which provides in situ monitoring of the temperature at the laser focus plane, are integrated within the laser scanner unit. The PMMA substrate and the silicon master stamp are fixed in a pneumatic stage, applying a constant pressure. There are two basic operation modes of the system: constant laser power or constant heating temperature. In our case, the temperature regulation is chosen in order to achieve a homogeneous temperature distribution at the contact surface. Utilizing an F-Theta objective lens (Fisba Optik) with a focal length of 163 mm, the size of the elliptical laser focus spot on the work plane is 0.55 mm × 0.7 mm. Attributed to the applied scanner system, the maximum laser processing area can reach 100 mm × 100 mm.
Before replication, a silicon master stamp was fabricated. Via electron beam lithography and reactive ion etching (RIE), the DFB corrugations with grating periods ranging from 195 nm to 450 nm, a height of ∼120 nm and a duty cycle of 75% were generated. Via aligned UV-lithography and subsequent RIE on the same wafer, basins for the DFB lasers with a height of 1.2 μm were completed. A thin anti-adhesion layer was then deposited on the wafer to facilitate the polymer substrate detachment.13
For the replication process, a 2 mm-thick PMMA substrate (Evonik, Plexiglas® XT) with a size of 30 mm × 30 mm was positioned on selected corrugations of the silicon master stamp. The following process parameters resulted in the highest-quality replication: a heating temperature of T = 180 °C, a laser scan velocity of v = 40 mm s−1, a clamping pressure of p = 0.1 MPa and a hatch distance (offset between two neighboring laser tracks) of Δx = 300 μm. To achieve a homogeneous replication, each substrate was treated twice by the laser beam: firstly perpendicular to the grating orientation, as shown in Fig. 1(a), and secondly parallel to the grating orientation. The replication process took about 5 min for the replication of an area of 40 mm × 40 mm. After replication, the clamping pressure was released. The PMMA substrate was cooled down with a nitrogen spray gun and separated from the silicon master stamp. Fig. 2(a) and (b) show a microscope image and a scanning electron microscope image on PMMA of a grating with a period of Λ = 400 nm. The grating structures fabricated via laser-assisted replication show a high fidelity over the whole molding area. The replicated quality was similar to thermal nanoimprint lithography, as shown in Fig. 2(c). However, the laser-assisted replication process took a much shorter time compared to the 45 min-long TNIL process. Alq3 doped with the laser dye DCM has been chosen as the active material. It forms a very efficient Förster energy transfer system and exhibits an excellent long-term stability. Evaporating 250 nm Alq3 doped with 2.8 wt% DCM onto the defined grating fields finally yielded the organic DFB laser pixels. The used stencil shadow mask was fabricated by UV-lithography and nickel electroplating.14
Fig. 3(a) shows the color-encoded spatially resolved lasing wavelength from a PMMA chip containing 9 laser pixels with individual lateral dimensions of 500 μm × 500 μm and an interspacing of 500 μm. The grating period of the DFB corrugations varies from 370 nm to 450 nm in steps of 10 nm from the outermost left pixel to the outermost right pixel. The chip was probed with a resolution of 100 μm. The laser emission wavelength did not show any deviation on the area of a single laser pixel within the spectral resolution of the setup (approximately 0.5 nm). This indicates a very uniform replication of the nanogratings in PMMA. The corresponding laser emission spectra and the laser threshold values for the TE0-modes are shown in Fig. 3(b) and (c). The blue-shifted TM0-mode laser peaks identified with a polariser can be detected at λ = 630.4 nm and λ = 643.6 nm. These peaks originate from the lasers with grating periods of Λ = 400 nm and Λ = 410 nm. The higher laser threshold from the laser pixel with a grating period of 450 nm is attributed to the lower gain coefficient at the emission wavelength of 712.5 nm.
For being suitable for LOC spectroscopic applications, the organic semiconductor lasers are usually based on first-order DFB gratings for the emission of light in the chip plane only. By introducing a waveguide onto the chip, the first-order organic laser emission can be efficiently coupled and guided to the analyte sites. PMMA chips with deep ultraviolet (DUV)-induced waveguides have been fabricated previously.11,13 In this work, we fabricated the active grating and waveguides altogether via laser-assisted replication and evaporated Alq3:DCM on both of them to build a coupled edge-emitting organic laser on chip. This novel configuration allows for a one-step fabrication of the laser and waveguide without mix-and-match pattern-related defects.36 Besides, the direct connection between the laser and waveguide made from the same active material will facilitate an optimum coupling efficiency.
Different gratings with lateral dimensions of 500 μm, interconnected by 300 μm-wide waveguide structures perpendicular to the grating orientation, were simultaneously fabricated in 1.2 μm-deep basins on the PMMA chip. The grating periods for the first-order organic DFB laser were chosen to be Λ = 195 nm, Λ = 200 nm, and Λ = 205 nm, as marked in Fig. 4(a). A 250 nm-thick layer of Alq3:DCM was evaporated on the defined grating and waveguide, thus allowing for an optimum light coupling.
The experimental setup for the chip characterization is schematically depicted in Fig. 4(b). The pump laser and the detection system were the same as used for the characterization of the surface-emitting organic lasers, but we changed the detection plane according to the chip orientation. The excitation spot diameter on the sample surface was ∼100 μm. In order to limit laser degradation in the ambient atmosphere, we set the excitation repetition rate as low as 100 Hz. Fig. 4(c) shows the laser spectrum of a DFB laser with a grating period of Λ = 200 nm. The laser emission at λ = 645.5 nm was detected at the chip facet using a multimode optical fiber (Ocean Optics, P400-3-UV-VIS). A stronger background due to the Alq3:DCM fluorescence than in the case of the surface-emitting lasers is observed. This can be explained by the fact that the fluorescence is coupled into the waveguide with comparable efficiency to the laser radiation. In the case of surface-emitting lasers, the fluorescence is almost not detected as it is emitted in all directions. The corresponding laser threshold was measured to be 145 nJ per pulse. This higher threshold can be explained by the laser being pumped at a larger excitation spot size than for the surface-emitting lasers.
In comparison, applying 2 s-long punctuated heating resulted in an expansion of the heat-affected zone on the silicon stamp and a consequently enlarged replication area. As shown in Fig. 5(b), an extension was measured as ∼3.8 times that of the laser focus spot size.
We verified the versatility of the localized replication by the fabrication of pre-selected laser pixels. Fig. 5(c) shows a partial replication from the silicon master stamp with gratings in periods of Λ = 390 nm, Λ = 400 nm, Λ = 410 nm and Λ = 420 nm. Each pixel has a dimension of 500 μm × 500 μm with an interspacing of 500 μm. A 2 mm-broad space was excluded from the laser writing path from left to right on the chip. As a result, we observed an unstructured area with a width of 1.8 mm between the replicated structures. The slight difference between the size of the unstructured area and the non-irradiated area is attributed to the heat conduction in the silicon master stamp. The spatially resolved lasing wavelength distribution revealed one completely omitted and one only partially available laser pixel. The latter had a clearly defined border. The corresponding laser pixel spectra are shown in Fig. 5(d).
As previously mentioned, a great advantage of the localized replication is the subsequent fabrication of nanostructures with already existing photonic, fluidic or electronic components, which remain unaffected during the fabrication process. We demonstrated this by replicating the same structures twice on a single 2 mm-thick PMMA substrate and performing two successive replication processes at a distance of 10 mm. Each replicated area was defined to be 5 × 20 mm2 without overlapping each other, as shown in Fig. 6(a). Fig. 6(b) shows a photograph of the finished laser pixels on the PMMA chip, which can be clearly identified by the interference effect. A 250 nm-thick Alq3:DCM layer was evaporated on top of the chip to check the laser behavior and determine the replication quality. All the laser pixels showed homogeneous laser emissions throughout the whole pixel area with corresponding wavelengths according to their DFB grating periods. Laser pixels featuring the same grating period revealed comparable characteristics, e.g., the laser thresholds of the laser pixels with a grating period of Λ = 420 nm were measured to be 17.3 nJ per pulse and 14.8 nJ per pulse, both emitting at the same laser peak wavelength of λ = 670 nm. The existing grating structures were not influenced by the subsequent replication process. This can be widely useful for LOC and other integrated optics applications. The inexpensive fabrication of identical nanostructures without repetitive construction on a master stamp is shown to be possible.
Footnotes |
† Currently with TRUMPF Scientific Lasers GmbH + Co. KG, 85774 Unterföhring-München, Germany. |
‡ Currently with DTU Nanotech, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark. |
§ Currently with Carl Zeiss AG, Corporate Research and Technology, 07745 Jena, Germany. |
This journal is © The Royal Society of Chemistry 2014 |