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©
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1101
www.advmat.dewww.MaterialsViews.com
 C  OMM UNI   C AI   ON
Nikos Vasilantonakis, Konstantina Terzaki, Ioanna Sakellari, Vytautas Purlys, David Gray,Costas M. Soukoulis, Maria Vamvakaki, Maria Kafesaki, and 
 
Maria Farsari*
Three-Dimensional Metallic Photonic Crystals with OpticalBandgaps
N. Vasilantonakis, K. Terzaki, Dr. I. Sakellari, V. Purlys,Dr. D. Gray, Pro. C. M. Soukoulis, Pro. M. Vamvakaki,Pro. M. Kaesaki, Dr. M. FarsariInstitute o Electronic Structure and Laser (IESL)Foundation or Research and Technology - Hellas (FORTH)N. Plastira 100, 70013 Heraklion, GreeceE-mail: marsari@iesl.orth.grN. Vasilantonakis, K. Terzaki, Pro. M. Vamvakaki, Pro. M. KaesakiDepartment o Materials Science and TechnologyUniversity o CreteHeraklion, Crete, GreecePro. C. M. SoukoulisAmes Laboratory and Department o Physics and AstronomyIowa State UniversityAmes, IA 50011, USA
DOI: 10.1002/adma.201104778
Over the last ew years, there has been an increasing interestin nanoscale metallic photonic crystals (PCs), i.e., periodic sys-tems o metal nanostructures. This interest is connected mainlywith the potential electromagnetic unctionalities o these struc-tures, which are not observed in bulk materials.
[1–3]
MetallicPCs signicantly modiy the properties o light with wavelengthclose to their periodicity, resulting in potential applications inscientic and technical areas such as lters, optical switches,sensing, imaging, energy harvesting and photovoltaics, cavitiesand ecient laser designs.
[4]
Studies o metallic PCs have mostly concentrated on micro-wave, millimeter wave and ar-inrared requencies.
[5–9]
At theserequencies, metals act like nearly perect refectors and haveno signicant absorption problems. There is an interest to ab-ricate 3D metallic PCs at ar-inrared and optical requencies,usually using the woodpile geometry,
[10]
to produce ecientthermal emitters and photovoltaic devices, through tailoringtheir absorption spectrum.The main reason or the current lack o 3D metallic PCs atoptical wavelengths is that the abrication o three-dimensionalmetallic, high resolution structures is a challenging task.Most o the 3D, submicron-scale metallic PCs that have beenobtained so ar are based on metal inltration o sel-organizedinverse opal structures.
[11–13]
This kind o structures do notallow abrication control o long-range monocrystals, due to thesel-organization underlying approach. Some eort has beenmade to directly abricate metallic 3D structures using multi-photon reduction o metal ions. The quality o the structures,however, has been compromised by the reduced transpar-ency o the metal ion solutions at the laser wavelengths used(500–800 nm).
[14,15]
Metallic woodpile structures have also beenrealized experimentally at micron wavelengths using traditionallithographic techniques.
[16–18]
However, lithographic techniquescan accommodate only a very limited number o layers, andaligning each layer with the previous one is not a trivial issue.To date, the most popular and successul method or theabrication o 3D metallic nanostructures is the preparation o 3D dielectric templates using Direct s Laser Writing (DLW),and their subsequent metallization.
[19–21]
DLW by multiphotonpolymerization is a direct laser writing technique that allowsthe construction o 3D structures with resolution beyond thediraction limit.
[22–24]
The polymerization process is due tononlinear absorption within the ocal volume, initiated by aocused ultraast laser beam. Employing laser intensities thatare only slightly above the nonlinear polymerization threshold,structures with very high resolution can be made.
[25,26]
In classicDLW, the lateral resolution is limited to about 100 nm. Thisvalue obviously cannot compete with state-o-the-art electron-beam lithography, where 10 nm are readily accessible. How-ever, recent work using stimulated-emission depletion DLW
[27]
 has approached 50-nm lateral resolution, with potential oruture improvements. Moreover, the recent increased interestin optical metamaterials,
[28]
in connection with imaging appli-cations,
[29]
has given an additional boost in research on nano-sale metallic periodic systems.
[4,28]
When a positive photoresist is structured using DLW litho-graphy, the result is a bulk structure with voids in the desiredshape. These voids can be lled with gold using electroplating,
[30]
 an extremely simple and inexpensive setup. One merely appliesa bias voltage between a transparent electrode on the substrateand a macroscopic counter electrode within a beaker.When a negative photoresist is structured, the result is a die-lectric template. To metalize this template, one can use atomic-layer deposition o silica or titania onto it, ollowed by chemicalvapour deposition o silver.
[31]
The technique most commonlyused or the subsequent metallization o these templates, how-ever, is electroless plating (EP). EP is a airly simple process thatdoesn’t require any specialized equipment, and the metal depo-sition can be done without using any electrical potential.
[32,33]
 In general it is characterized by the selective reduction o metalions at the surace o a catalytic substrate immersed into anaqueous solution o metal ions, with continued deposition onthe substrate through the catalytic action o the deposit itsel.One approach is to use a standard photolithographic material,such as the negative photoresist SU8 or the abrication o thestructures, and subsequently activate their surace.
[34,35]
In thiscase additional processing, to enable the metal adhesion onthe surace, is required and the quality, structural integrity andresolution o the structures depends on the building material
 Adv.
 
Mater.
 
2012
,
24
, 1101–1105
 
1102
www.advmat.dewww.MaterialsViews.com
©
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
    C    O    M    M    U    N    I    C    A    T    I    O    N
and the surace processing step. The resolution and structureintegrity can be very good; however, as the density o the metalbinding sites on the structure cannot be controlled, the met-allization quality can vary. In addition, along with the suraceo the structures, the substrate is also activated; the metalliza-tion is thereore not selective, oten requiring an extra step toremove the structures rom the metalized substrate.
[35]
This isaddressed by an alternative approach, which employs a photo-polymer doped with the metal binding sites. In this case, themetallization is selective, the density and distribution o thebinding sites can be controlled, and the resolution, structuralintegrity, and metallization quality limitations derive only romthe photopolymer used.
[36]
To date, the DLW approach with sub-sequent metallization has been applied up to now with greatsuccess in the realization o inrared metamaterials.
[28,35,37]
Here, we report the nanoabrication o 3D metallic woodpilestructures with eatures below 100 nm, obtained by DLW andselective silver coating. The structures, which have cc geom-etry
[10]
and in-layer periodicity 600 nm, are abricated usingan organic inorganic, zirconium-silicon hybrid material dopedwith a metal-binding monomer, 2-(dimethylamino) ethyl meth-acrylate. They are subsequently metalized using electrolessplating. The metalized structures are shown to exhibit ohmicconductivity, comparable to pure silver. We also present hereexperimental and theoretical electromagnetic characterizationresults o the abricated structures, showing a cut-o at around300 THz (1
μ
m) and a second band gap inside the optical parto the spectrum, centered at 450 THz. To the best o our knowl-edge this is the rst time that metalized structures with suchresolution, ohmic response, and band gaps in the visible areabricated and characterized.In what ollows we discuss rstly the structure abrica-tion and metallization steps, we continue with the resistancemeasurements, which demonstrate the ohmic response o thestructure, and with the structural characterization, which dem-onstrates the long range-order characterizing our structuresand provides the geometrical eatures used in the simulations.Finally we discuss the experimental and theoretical electromag-netic characterization o the structures, through transmissionmeasurements and simulations, which reveal a bandgap in thevisible range.The photosensitive material used or the abrication o thethree dimensional photonic nanostructures is a zirconium-silicon organic-inorganic material doped with tertiary aminemetal-binding moieties.
[38]
Hybrid (organic-inorganic) mate-rials are a very popular class o photosensitive materials, asthey are easy to prepare, modiy and photopolymerize and,ater polymerization, they are optically, mechanically andchemically stable. As a result, the have ound many applica-tions in 3D photonic and biomedical devices.
[39,40]
In addition,hybrid materials chemistry provides the possibility o the inclu-sion o unctional groups, such as nonlinear optical moleculesand quantum dots.
[41,42]
Building on our previous work on thesynthesis and DLW processing o a silicon-zirconium hybridmaterial,
[43,44]
we have added methacrylate moieties by addinga 2-(dimethylamino) ethyl methacrylate (DMAEMA) monomer,capable o participating in the photopolymerization step toincorporate covalently bound metal-binding groups in the 3Dstructures.
[38]
The main materials used here or the synthesis o photopolymer were methacryloxy-propyltrimethoxysilane(MAPTMS, 99%), dimethyl- aminoethyl methacrylate (DMAEMA,
>
99%) and zirconium
n
-propoxide (ZPO) 70% solution in 1-propanol. The molar ratios were 7:3 or MAPTMS/ZPO and 3:7or DMAEMA/MAPTMS. MAPTMS was rstly hydrolyzed byadding HCl (0.1 M) at a 1:0.1 ratio and the mixture was stirred or20 minutes. Next, ZPO was mixed with DMAEMA and the mix-ture was stirred or 15 min. The MAPTMS sol was gently addedto the stirred ZPO sol and the mixture was stirred or 30 min.Finally, the photoinitiator 4,4-bis(diethylamino) benzophenonewas added at a 1% w/w concentration to the nal solution. Thesolution was ltered using 0.2
μ
m syringe lters. Beore struc-turing, a small droplet o the composite solution was placedon a on a 100 micron thick glass slide and heated at 50 ºC or30 min. Ater DLW processing, the sample was developed and thematerial not exposed to the laser radiation removed by immer-sion in a 7:3 isopropanol/1-propanol solution. The metallizationprocedure has been described in detail previously.
[38]
For the 3D structuring a Ti:Sapphire emtosecond laser(800 nm, 75 MHz,
<
20 s) was ocused into the photopoly-merisable composite using a high numerical aperture ocusingmicroscope objective lens (100
×
, N.A.
=
1.4, Zeiss, PlanApochromat). Sample movement was achieved using piezoelec-tric and linear stages, or accurate and step movement, respec-tively (PI). The whole DLW setup, which is described in detailin Re. [45], was computer-controlled using the 3DPoli sotware.Here, the average laser power used or the abrication o thehigh-resolution structures was 18 mW, measured beore theobjective, while the average transmission to the sample was20%. To avoid contact with the lens immersion oil, all struc-tures were abricated upside down with the glass substratein contact with the oil. They were built layer-by-layer startingrom the top with the last layer adhering to the substrate. Thisway, the laser beam did not cross an already polymerized layer,causing second polymerization or beam distortion.In order to measure the conductivity o the metalized struc-tures, solid bulk dielectric boxes were created and metalized viaelectroless plating, keeping the same conditions as in the wood-pile structures, and the resistance at the aces o those boxes wasmeasured. The equipment used or the measurement was a Tek-tronix 370 curve tracer, which monitors the current,
, or eachspecic voltage,
, applied between the two metallic needles o thetracer which are placed on the samples. Modiying the voltage weobserved the linear
I–V 
response o the structures, and thus theirOhmic behavior, with average resistance R
=
(3.46
±
0.21)
Ω
. Cal-culation o the resistivity,
ρ
, taking into account the needle sizeand the thickness o the metal gave
ρ
 
=
(1.75
±
1.15)·10
7
 
Ω
·m,and, thus, conductivity
σ 
 
=
1/
ρ
 
=
(5.71
±
3.01)·10
6
 
Ω
1
·m
1
. Thisresult is close to the conductivity o pure silver, which is6.3·10
7
 
Ω
1
·m
1
(DC value). The thickness o the metal wasestimated rom SEM images o structures beore and atermetallization and was ound to be in the range
30–50 nm.
Figure
1 shows the Scanning Electron Microscope (SEM)pictures o some typical metalized woodpile structures with twodierent periodicities, showing the fexibility and the high reso-lution that can be achieved using this abrication technology. Inorder to achieve maximum resolution, the lowest intensity thatwas enough to abricate ully 3D structures was used.
 Adv.
 
Mater.
 
2012
,
24
, 1101–1105
 
1103
www.advmat.dewww.MaterialsViews.com
©
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 C  OMM UNI   C AI   ON
is actually revealed by the square symmetry o the diractionpattern observed.
[46]
The sharpness o the diraction spots indi-cates the long-range order in the crystal.As already described by several groups,
[46,47]
diraction chan-nels or normal incidence are open when the incident wavevector
k
is larger in magnitude than any o the 2D reciprocallattice vectors,
g
, o the planes parallel to the crystal surace.A diraction cuto is observed whenever
|
g
|
 
=
 
|
k
|
. For a square
Figure
2 shows a metalized woodpile structure with 600 nmperiodicity abricated using 1.90 mW laser power. This struc-ture has 3 unit cells (12 layers) thickness and its eatures are inthe order o 100 nm.For the transmission measurements a white light sourcepumped at 1064 nm (Fianium) was used. The light beam wasocused normally to the sample surace using a 7.5 cm ocallength lens, while the transmitted light was collected using anoptical spectrometer (Ocean Optics S2000). The hal-openingangle o the incident light was 5
°
, assured by iris diaphragms.The diameter o the ocused beam in the sample was 24
μ
m,while the measured nanostructure surace normal to the beamwas 40
μ
m
×
40
μ
m. As the size o the sample’s surace wascomparable to the beam spot diameter, sample alignment wasdicult and critical. To check the alignment, but also to checkthe quality o the sample, the diraction pattern in the refectedwaves produced by the structure when illuminated by the whitelight beam was used.
Figure
 
3
shows a typical such dirac-tion pattern. To understand the diraction pattern one shouldnote that the woodpile structure presents the {001} amily o planes parallel to the crystal surace - the direction normal tothese planes is reerred as
Γ 
, which is the one studied. Inthese planes the structure presents a square symmetry, that
Figure 1.
Metalized woodpile structures at 900 nm (a) and 600 nm(b) periodicity. The value at the bottom let corner depicts the averagethickness o the rods.
Figure 2.
Perspecitive view o a 600 nm periodicity and 3-unit-cell (12-layer) thickness woodpile structure.
Figure 3.
Characteristic cross diraction pattern o the refected wave dueto the structure geometry.
 Adv.
 
Mater.
 
2012
,
24
, 1101–1105

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