5. Nanostructure fabrication 5.1 Top-down nanofabrication 5.2 Bottom-up nanofabrication Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 1 Nanostructure fabrication Top-down nanofabrication Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 2 Introduction • Motivation: – – – – Concept of top-down fabrication processes Materials, devices, limitations Differences between scientific and industrial nano-fabrication Examples • Structure – Part I: Basic concept, clean room architecture, lithography (ca. 90 min.) – Part II: Deposition, etching methods and back-end fabrication • References freely accessible – Henderson Research Group https://sites.google.com/site/hendersonresearchgroup/helpful-primers-introductions – Review paper: Garner C M, Lithography for enabling advances in integrated circuits and devices. Phil. Trans. R. Soc. A. 2012; 370:4015. – Brochures by MicroChemicals GmbH http://www.microchemicals.com/downloads/brochures.html Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 3 Terms and Definitions • Microsystems – Dimensions of the functional structures in µm – aka Micro Electro Mechanical System, MEMS – Fluidics („lab-on-a-chip“), optics, many sensors and actuators – Integrated Circuits (IC): DRAM, flash memory, CMOS processors • Nanosystem (NEMS) – Nano-structure: two dimensions < 100 nm, e.g. electronic gates, photonic crystals, quantum dots, apertures – ultrathin layers < 100 nm, e.g. double-hetero or quantum-well-structures, extremely efficient, selective mirrors, filters • Top-down / bottom-up – Top-down: optimized microfabrication methods – Bottom-up: self-organized, chemical processes (e.g. Carbon Nano Tube growth) Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 4 Industrial Chip Fabrication Recovery of Si, wafer manufacturing; Frontend: Deposition, Lthography, Etching; Back-end: Probing, Dicing, Bonding, Encapsuation, Burn-in and Test. Philipp Altpeter Process cycle for the manifacturing of semiconducting chips (Hansch. Technik in Bayern; 04/2011.) Nano 1 ─ 5.1 Top-down nanofabrication 5 Concepts and Classification • Patterning – Fotolithography (reproducing) – Charged particle beam lithography (serial wiriting) – Nano-imprint • Deposition (additive methods) – Physical or chemical Plasma-depositions – Evaporation, MBE, ALD – Spin-on – Electroplating • Etching (subtractive methods) – Dry-etching (Plasma enhanced) – Wet-etching • Basic concepts of top-down fabrication. a) patterning b) deposition OR etching c) Resist removing OR lift-off Back-end – Chip- and wire bonding, Encapsulation Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 6 Clean room technology • • • What means ‚clean room‘? → avoiding and filtering of air particles Particles with size of 1/10 of the minimal structure dimensions are critical Possible praticle sources – Air → circulating through filters by blowers/ventilators – Contaminants within chemicals → clean materials (VLSI, ULSI standard) – Abrasion from machines → grey-rooms contain infrastructure – Contact contamination (e.g. impure tools) – Clean room personnel – emmits 35 % of all particles! → „protection“ clothes, careful behavior Movement type Emission of particles (dP > 0,5 µm) per minute Regular clothes • Clean room clothes Sitting (no movement) 3 · 105 7 · 103 Head movement 6 · 105 104 Body movement 106 3 · 104 Slow walk 3 · 106 5 · 104 Fast walk 6 · 106 105 Büttgenbach S. Mikromechanik. Stuttgart: Teubner; 1994. Regulated environment (temperature, ventilation cycles, air humidity) Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 7 Clean room technology • Air flow and filtering in clean rooms Partikelzahl pro ft3 Partikelzahl pro m3 Ceiling Floor Cross-sectional drawing of an conventional clean room, air flow and ventilation. Büttgenbach S. Mikromechanik. Stuttgart: Teubner; 1994. Partikelgröße / µm – DIN EN ISO 14644: ISO class n → less than 10n particles smaller 0,1 µm pro m³ – US Fed. standard 209b: US class n → less than n particles smaller 0,5 µm pro ft³ Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 8 Overview lithography methods • reproducing methods – shadow impact fotolithography (smallest features ca. 1 µm) – projection exposure (Deep-UV: 32 nm) – X-ray lithography w/ synchrotron radiation (sub-µm, extremly high aspect ratio, i.e. vertical to lateral dimensions) • imprint, transfer printing… (soft lithography) • direct writing methods – Laser Direct Imaging (sub-µm) – electron-beam lithography (10 nm) – Focused Ion Beam (FIB) lithography or milling Philipp Altpeter templates mask, reticle (scaling 1:4) stamp CAD drawing from PC Nano 1 ─ 5.1 Top-down nanofabrication 9 Photolithography • • • • Reproduction of structures in photo-sensitive films (photoresist, PR) Light source: mercury arc lamp – Spectral lines in regard to the absorption characteristics of the PR: I line @ 365 nm, H line @ 405 nm, G line @ 436 nm Photomask as template: patterned Cr film on a (UV transparent) quartz plate Shadow impact illumination (see below), projection printing Principle of shadow impact lithography. Madou M. Fundamentals of Microfabrications. Boca Raton: CRC Press; 1997. Philipp Altpeter UV part of the Hg spectrum. Koch Ch, Rinke T J. Lithography. Ulm: MicroChemicals; 2006. Nano 1 ─ 5.1 Top-down nanofabrication 10 Photolithography Maskaligner Karl Suss MJB 3 Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 11 Photoresist technology • Positive PR (solubility of exposed areas increased) – Composition: Novolak resin, photo-active compound (DNQ), solvents • Negative PR (solubility decreased) – Crosslinking or polymerization (chain growth) induced by proper irradiation – Slightly reduced resolution through diffusion of developer and swelling of structures – Chemical amplification: photon generates acid catalyst which initiates depolymerization; quencher added to quench the diffusion of the catalyst After Exposure After Development Alteration of solubility of a CA positive-tone resist over the course of the process. Philipp Altpeter Profile characteristics of positive-tone PR (a) and negative-tone PR (b). Nano 1 ─ 5.1 Top-down nanofabrication 12 Typical process flow • Pretreatment, adhesion promotion Surface chemistry: hydrophilic → hydrophobical (non-polar) by means of: using a primer, heating, oxygen-plasma • Spin coating (defines the thickness of the PR layer considering the viscosity) • Softbake (evaporating solvents) • Exposure (photo-chemical activation) • Post-Exposure-Bake, PEB (increasing crosslinking; finishing the photo-reaction) • Development (Dissolution either of exposed or non-exposed areas) • Hardbake (better adhesion and chemical-mechanical stability) • De-scumming (Etching of resist residues in O2-plasma) Philipp Altpeter Principle of resist coating by spinning. Nano 1 ─ 5.1 Top-down nanofabrication 13 Basic chemistry of mid-UV, positive-tone PR DNQ (unexposed) dissolution inhibitor h·v +H2O DNQ (exposed) dissolution promotor Philipp Altpeter Chemical structure of a conventional positive resist. Koch Ch, Rinke T J. Lithography. Ulm: MicroChemicals; 2006. Nano 1 ─ 5.1 Top-down nanofabrication 14 Physical resolution limits • Resolution: min. resolvable distance between two points (see Rayleigh criterion). bmin ≈ 1,5 ⋅ λ ⋅ (g + t R 2) • bmin: minimal feature size g: proximity gap tR: resist thickness Light diffraction, proximity illumination – contact mode – layer thickness – edge bead – particles, bubbles Proximity distance caused by edge bead of the coated resist film. Intensity distribution depending on wavelength, slit width, gap Koch Ch, Rinke T J. Lithography. Ulm: MicroChemicals; 2006. Philipp Altpeter Diffraction pattern by a slit aperture from near field to far field, a) Fraunhofer diffraction, b) Fresnel diffraction. Tipler P A. Physik. Heidelberg, Berlin: Spektrum; 1994. Nano 1 ─ 5.1 Top-down nanofabrication 15 Consequences of light diffraction SEM micrograph: diffraction pattern reproduced in a photo resist film after development; Slit width in photomask: 4 µm. Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 16 Resist-based resolution limits • Contrast and sensitivity (diffraction → grey areas) Low contrast: resist edges shallow, poor defined D0 T(D) = T 0 ⋅ γ ⋅ ln D T(D): residual resist after development Contrast curve of a standard positive resist; Consider logarithmical abscissa. D0 1 γ= = log log D0 − log D1 D1 • • −1 γ: contrast Do: exposure dose D1: threshold dose Smallest achievable structure width by means of shadow impact litho: ≈ 1 µm for DUV and below: high efficient, chemical amplified (CA) resists required Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 17 Resist optimization • Quality of a high-end CA-photoresist given by: Z = R³ x LER² x S R: ultimate Resolution LER: Line Edge Roughness S: Sensitivity → throughput • Chemical amplified (CA) resists limited by the ‚Triangle of death‘ Sensitivity Acid diffusion length Line Width Pitch Resolution vs. Line Edge Roughness. • half-pitch = max. Resist thickness Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 18 Projection exposure • • Structures from photo mask will be demagnified and printed through a reduction lense Wafer stepper moves wafer from each position to the next where the illumination takes place bmin ≈ k 1 ⋅ λ NA bmin: minimal feature size k1: prefactor, ca. 0.6 in case of incoherent light NA: Numerical Apertur of the lense system • • • DOF ≈ k 2 ⋅ λ NA 2 k2: prefactor, ca. 0.5 Depth of Focus: consider resist thickness and complex topologies! Advantages: better resolution, more different structures (layer levels) on one photomask Disadvantages: expensive, Schematic of simplified step-and- repeat projection exposure tool system. http://henderson.chbe.gatech.edu/Introductions/microlithography%20intro.htm time consuming exposure Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 19 Lithography evolution • • • • high intensity and low wavelength light sources required for high resolution ArF excimer laser (193 nm, DUV) and immersion litho (increase of NA up to 1.3) optical transitions in highly elaborated plasma sources for EUV (13.5 nm): bmin<20nm very expensive! Ultra-high vacuum condition, multi-layer mirrors instead of lenses to avoid light absorption and complicated mask technology (phase masks, compensation structures) Ultra-modern lithography tool of ASML working at Extreme UV (pricing > 60 M€). Hansch. Technik in Bayern; 04/2011. Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 20 Laser Direct Imaging • • Laser Direct Imaging (LDI): monochromatic, coherent, gaussian Laser beam (375 or 405 nm) is scanning across the surface (Vector-scan) Beam deflection by means of an acousto-optical deflector (AOD) in combination with motorized stage Software Transducer generates acoustic wave through the quartz crystal Refrective index n alters periodically in order of the density variation Bragg diffraction → Bragg angle proportional to f of the acoustic wave (Θ ~ ∆f) Intensity depends on RF power of the transducers. • • Typical specs: Spot size = 1…3 µm Beam positioning in nm range Rayleigh length 2…20 µm Control via PC, design defined by CAD Philipp Altpeter Beam path of a Laser Direct Imaging system. By courtesy of Anze Jeric (LPKF). Nano 1 ─ 5.1 Top-down nanofabrication 21 Standing wave issues • Advantages: maskless, no diffraction on photomask structures, usually better resolution achievable flexible, Design quickly and easily adaptable Dose variation / dose test doable with one exposure • Disadvantages: Riffled edges (see below) caused by standing waves reduced resolution Large areas need a long over-all exposure time Stitching error at extended structures (e.g. wave guides or channels) ∆z = (λ / 4) n-1 Riffled sidewalls (top) caused by illumination with monochromatic light. Model of standing waves within photo resist (right). Madou M. Microfabrication. Boca Raton: CRC Press; 1997. Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 22 Electron beam lithography • Requirements: Scanning Electron Microscope (SEM) with pattern generator, electrostatic beam blanker and a PC to control the system Abbe resolution criterion: d min = k 1 ⋅ Beam path of a SEM with Thermal-Field-Emitting (TFE) cathode. Manual LEO-FE-REM 982. λ n ⋅ sin α dmin: min. dimension n · sin α: Numerical Aperture (NA) λ: wavelength Free, accelerated electrons → very small De Broglie wavelength e.g. at 10 keV << 1 nm! Comparison: Hg transition at 365 nm (I line), 1. Kathode and even EUV at 13.5 nm 2. Suppressor electrode (housing) → charged particles (like electrons) excellently focusable and deflectable! Philipp Altpeter 4. Extractor electrode 5. Anode 7. Condensor lense 10., 11. Objective lense 12. Sample Leaving area and amount of Secondary Electrons (SE) depend on topography (edge effect). Nano 1 ─ 5.1 Top-down nanofabrication 23 Electron beam lithography • • • • • • Beam creation with Primary Electrons (PE) Focusing of the PE beam by means of electrons optics (electromagnets and aperturs) Scanning across the sample surface via deflection coils Emission of Secondary Electrons (SE) at the e-beam spot Amount of SE depends on topography (→ edge effect) Detector „soaks in“ SE and produces an intensity signal depending on the surface profile How imaging of scanning electron microscopy works. Hawkes P W. Scanning Electron Microscopy. Heidelberg: Springer; 1985. Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 24 Focusing of charged particle beams • • • inhomogenous B field along pole shoes of electromagnets serves as a convex lense for electrons (or ions) If electrons (coming from the primary beam) have a component of the velocity vector perpendicular to the B field v┴ , they sense the Lorentz force F = - e (v × B) Focus adjustable by variation of the field strength: f ~ B02 Aberrations of optical systems. Hawkes P W. Scanning Electron Microscopy. Heidelberg: Springer; 1985. Schematic of an electron lense. Hawkes P W. Scanning Electron Microscopy. Heidelberg: Springer; 1985. • Typical aberrations – Spherical aberration (Öffnungsfehler) – Chromatic aberration (Farbfehler) – Astigmatism, cylinder asymetries – Diffraction error Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 25 E-beam lithography: exposure methods Fixed Beam Moving Stage • Software turns design into polygons • Pattern generator scans these polygons one after another and from pixel to pixel • Step size (between pixels) depends on write field size and address range of the pattern generator • excellent resolution, but stitching errors at extended structures, low throughput, low-cost Philipp Altpeter • Software turns design into polygons • smart alignment of beam and aperture to expose the whole area of one polygon • Beam stationary, stage is driving • Trace of the stage is defined by vectors and stage coordinates • high throughput, but expensive hardware • for high resolution, interferometer required; NO stitching Nano 1 ─ 5.1 Top-down nanofabrication 26 E-beam lithography: vector scan method D = J ⋅ t Dwell E-gun Anode Alignment coils D: dose; typ. 100 µC · cm-2 → resist properties, developer temperature, substrate J: probe current density → cathode, acceleration voltage, aperture diameter tDwell: dwell time → data bus frequency, beamblanker, deflection coils resp. scan electronics Condenser lens Aperture Beam blanker electron beam Pattern generator 50 pA Objective lens 200 µm Scan coils Write field size and step size → adress range, e.g. 16 Bit DAC (216 = 65536), WF: 100 µm → Step size: 1.5 nm 3 nm Vector scan patterning with a conventional SEM. Trainingsunterlagen Fa. Raith. Philipp Altpeter Matching of microscope magnification and write field size Definition of write field. Trainingsunterlagen Fa. Raith. Nano 1 ─ 5.1 Top-down nanofabrication 27 EBL vector scan: stitching errors Stage movement WF1 Shift in X (ca. 200 nm) Gap due to Zoom error (0.5 %) Write Field Border WF2 Philipp Altpeter WF Edge Length 100 µm Nano 1 ─ 5.1 Top-down nanofabrication 28 Fixed beam moving stage Laser interferometric stage. Trainingsunterlagen Fa. Raith Precise positioning by means of an interferometer. Hoffmann J. Taschenbuch der Messtechnik. München, Wien: Carl Hanser; 2002. Feedback Philipp Altpeter FBMS: travelling stage, ‚resting‘ beam; feedback from interferometer to beam deflection. Nano 1 ─ 5.1 Top-down nanofabrication 29 Shaped beam lithography • • • beam shape defined by a system of apertures instead of scanning pixel by pixel ‚large‘ areas are quickly exposed specialized, complicated system and expensive! Philipp Altpeter Shaped e-beam lithography by Leica Microsystems Lithography GmbH Nano 1 ─ 5.1 Top-down nanofabrication 30 Typical SEM with e-beam attachments LEO FE-REM GEMINI 982 Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 31 Resolution limits of electron beam lithography • Theoretical limit given by the De Broglie wavelength of the PE • But: backscattered (BSE) and secondary electrons (SE) cause an exposure too → proximity effect BSE: E > 50 eV SE: E = 2 … 20 eV Tread depth of SE, around 3 nm • aberrations (s. slide #25), coulomb repulsion • Resist properties (contrast) most important: PMMA (positive; chain scission mechanism), PMMA HSQ, SU-8… (negative-tone) Silizium • interaction zone → atomic number and acceleration voltage Philipp Altpeter Beam diameter d shrinks with higher acceleration voltage d 10 kV d d 20 kV Scattering events simulated by Monte Carlo in PMMA and Si depending on acceleration voltage. Nano 1 ─ 5.1 Top-down nanofabrication 32 Cathodes / Electron emitters • Emitter types: – thermal emission (Heizkathode) Requirements: low work function, thermally stable → W optimal material: ceramic LaB6 (lower work function than W, very small emission area) – (cold) field emission: E-field causes tunneling of electrons Advantage: smallest, atomic emission area → almost no chromatic aberrations and an excellent, small spot Disadvantage: unstable emission current, extremly high vacuum required – best of both: thermal field emission (TFE of Schottky cathode). Tip is covered with Zircon Oxide (W/ZrO) to reduce work function SEM images of an TFE cathode. Left side: tip surrounded by the suppressor electrode. (Mag. 200x); Center: tip diameter ≈ 300 nm; Right: foto of the whole device. Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 33 Enhancements of e-beam lithography • Focus electron beam induced processing Using precursor gases for direct etching or deposit of materials Left side: Principle of electron beam induced deposition (EBD). Center: Image of the injection needles. Right: SEM micrograph of the needle at 20x magn. Trainingsunterlagen u. Handbuch der Fa. Raith. Nanomanipulator. Right side: Drawing of the complete device (Handbuch Fa. Raith); left: SEM image shows a nanomanipulator bending a GaAs pillar (ca. 30.000x magn.), ∅ tip ≈ 300 nm, ∅ pillar ≈ 1 µm. • Nanomanipulator – moves free-standing nano-structures mechanically – electrical probing of nano-devices – Smallest step size < 4 nm Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 34 Nanoimprint Lithography (NIL) • Substrate surface coated with a polymer (a) • Imprint template/stamp pushed into polymer (b) • • Polymer cures thermally or by UV radiation Remove of imprint tool, polymer image remains (c) • Critical challanges: low-defect template; polymer: good adhesion to wafer, no adhesion to imprint tool Principle of nano transfer printing. Fakhr O, Altpeter P, Karrai K, Lugli P. Easy Fabrication of Electrically Insulating Nanogaps by Transfer Printing. Small 7 2533 (2011) Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 35 Example1: Mix & Match • • • • Substrate: Silicon-On-Insulator (SOI); device based on Metal-Oxide-Silicon (MOS) Field-Effect-Transistor (FET) Mix and match: combination of both, fotolithography and EBL quasi-metallic structure through extensive doping of source and drain (Silicon) thermal oxidation of Si and wet etching of SiO2: thinning! Wiring and bond pads hair Contact printing lithography pattern SEM image of a Silicon nanowire. Tilke A. Dissertation. München; 2000. e-beam pattern Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 36 Sense of the magnitude… Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 37 Example 2: laterally defined Double Quantum Dot (DQD) Chip carrier and bond wires (‚spider legs‘) QD QD (a) 20x magn. Nano magnet (Co), 2nd EBL step electric gates (Au), 1st EBL step (b) 50000x magnified SEM images of a quantum dot structure; (a) sample attached to carrier, (b) Co nano magnets, (c) Au gates in the center. Substrate: molecular beam epitaxy (MBE) grown heterostructure GaAs/AlGaAs Kupidura D. Dissertation. München 2009. (c) 2000x magn. Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 38 Example 3: suspended quantum dot structure • Additional etching steps required: anisotropic Reactive Ion Etching and isotropic sacrificial layer wet etching. Source Drain G1 G2 SEM images of a suspended double quantum dot (DQD) structure. Left image: top view. Right image: tilted at 85° Below: Process flow: starting from the heterostructure, followed by several lithography steps, suspended wire via sacrificial layer etching in the end. Rössler C. Dissertation. München 2008. Process flow Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 39 Example 4: high reflective Bragg mirror • • • • • 1-dimensional nano-structure (stack of layer) quarter wave Bragg reflector alternating double layer of GaAs (high index, 3.480) and Al0.92Ga0.08As (low index, 2.977, @ 1.064 um) or other material combinations like SiO2 / Ta2O5 deposited by Molecular Beam Epitaxy (MBE) or (epitaxial) Sputtering Interference of λ/4 double layers s. below. Top: principle of a Bragg reflector (batop.de/information/r_Bragg.htm) Right figure: schematic of an EBD grown reflector, cross-sectional SEM image and reflectance (meausered: ret dots; simulated: blue line) Cole et al. Nature Photonics 7, 644–650 (2013) Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 40 Example 5: photonic crystals • • • • • Photonic crystal: periodic, alternating structure of the refractive index Compared to the electronic nature of semiconductors → band structure etc. High-resolution EBL, perfectly shaped lattice elements needed anisotropic Silicon etching with a special EBL resist (ZEP) as soft-mask Shape and line edge roughness strongly defines the quality of these structures Different optical devices – such as: waveguides, beam splitter, resonators – fabricated by EBL (below); SEM image of a 1-dimensional waveguide with a small defined defect in the center (top left); simulated and measured data of the light transmission through this structure,w hich behaves like a filter (top right) Birner et al. Phys. Blätter 55 (1999). Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 41 Example 6: Electron Beam Deposition AFM tips • • • • Focussed Electron Beam Induced Deposition (FEBID) on the apex of a conventional AFM pyramide carbonic precursor decomposed by focussed electron beam into non-volatile and volatile products sharp pillar made of amorphous, diamond-like Carbon: strong and steady Application: e.g. measurement of roughness in deep trenches Down left: principle of Atomic Force Microscopy (AFM); from: the NanoWizard AFM Handbook, Fa. JPK, v1.3, 08/2005. SEM images of atomic EBD tips (right), courtesey of nanotools GmbH. ultra-sharp probes for atomic force microscopy length: up to 6,000 nm radius: 5 nm optical lever Philipp Altpeter Nano 1 ─ 5.1 Top-down nanofabrication 42
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