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A selection of research topics in semiconductor physics at the Cavendish Laboratories G A C Jones Cavendish Laboratory University of Cambridge Outline of talk • • • • Split gate technology Surface Acoustic Wave driven devices Site control of quantum dots Ultra high resolution lithography Split gate technology for 2D, 1D and 0D electronic devices (Wharam et al. J Phys C 21, L209 (1988)) Two-dimensional electron gas (2DEG) Material Growth by MBE 2DEG mobility in modulation doped structures Pfeiffer et al APL 55,1888 (1989) Quantum wire -ve drain -ve source Quantized Conductance in 1D •Making gate voltage more negative decreases well width and increases level spacing – depopulating energy levels one by one. -1V Number of occupied subbands EF −∆V 0V 4 2D(ii) 2D(i) 1D 3 Vg more negative→ -1V Wharam et al J Phys C 21, L209 (1988) Thomas et al APL 67, 109 (1995) 2 1 x wire Quantum dot drain source Examples of devices based on split gate technology Quadruple quantum dot Aharanov Bohm device with quantum dots Making connections to isolated electrodes Making connections to isolated electrodes Surface Acoustic Wave Driven devices Metallic surface gates 1 µm transducer, used to create a mechanical surface acoustic wave (SAW) SAW devices can be tuned to transport an integer number of electrons in each minimum, which leads to current quantisation. Metallic surface gates are used to define 1D channels. The spins of electrons in these channels can be used as qubits. Ohmic contacts SAW speed is ~2800 m/s. GaAs is piezoelectric, so a travelling electric wave is created. SAW driven single photon emitter hν SAW n i p hν Ef 3GHz SAW transducer 3GHz SAW transducer Quantum dots with non-invasive detectors Dual channel SAW device for investigating electron interactions and entanglement Magnetic gates 3nm Au + 20nm NiFe + 3nm Au Spin Manipulation Using Nanomagnets Nanomagnetic fingers designed to redirect an external field to a perpendicular direction have been fabricated. The magnetic field in the gap has been imaged with electron holography. An external field of 1 T leads to ~190 mT in the gap. It should therefore be possible to rotate injected electrons to . Similarly designed nanomagnets can also be used to create an alternating magnetic field for use in ESR-type experiments. InAs Quantum Dots for optical applications Motivation • Discrete density of states makes quantum dots ideal as single photon sources for quantum cryptography or optical quantum computation schemes Electrically Driven Single-Photon Source Zhiliang Yuan, et al. Science (2002) 295 102-105 P. Atkinson, Cambridge University, 2005 Stranski-Krastanov growth of InAs dots by MBE results in near-random dot distribution 1.2 ×10 9 cm-2 2.55ML at 0.01ML/s 515°C P(A)=2.1×10-7 mbar V/III flux ~ 450 P. Atkinson, Cambridge University, 2005 Site-control of dot nucleation • Electron-beam lithography to pattern small holes (diameter ~60-140 nm) • RIE etching (SiCl4)/ wet etching (weak sulphuric acid based) to etch pits ~1040nm deep • Resist removal (solvent rinses, oxygen plasma ashing) • In-situ low-temperature oxide removal by hydrogen plasma (preventing surface damage) pre-growth after H plasma treatment P. Atkinson, Cambridge University, 2005 Site-control of dot nucleation [110] pre-growth P. Atkinson, Cambridge University, 2005 after 10nm GaAs buffer after 2ML InAs dep Site-control of dot nucleation Good single dot occupancy Holes completely infilled Some double dot occupancy Dots on the verge of coalescing P. Atkinson, Cambridge University, 2005 No dots nucleating between patterns (less than the critical InAs thickness deposited) Photoluminescence Observation of photoluminescence from nucleated dots Data courtesy of Martin Ward, Toshiba Cambridge Research P. Atkinson, Cambridge University, 2005 Nanoimprint masters for sub-10 nm patterning M. S. M. Saifullah, Z. Zheng, W. T. S. Huck, D. Anderson, G. A. C. Jones & M. E. Welland, Unpublished data, (2005). Nanoimprint masters for sub-10 nm patterning M. S. M. Saifullah, Z. Zheng, W. T. S. Huck, D. Anderson, G. A. C. Jones & M. E. Welland, Unpublished data, (2005). Acknowledgements • • • • • • • • Dave Anderson Paola Atkinson Stephen Bremner John Griffiths Massaya Kataoka Dave Ritchie Saif Saifullah Martin Ward Collaborative projects with KAIST Towards 1nm lithography Prof H S Kim (Sun Moon University) is developing optics for a low-voltage, high-resolution, e-beam micro lithography column. Dr D. G Hasko (Cavendish), has been collaborating by providing expertise for the resist processing which requires a deeper understanding to achieve nanometer scale resolution. One student has spent several weeks in Cambridge working on this project learning resist processing etc. • Dr S B Lee (Hanyang University) is responsible for system integration of this tool and the Cavendish Lab has supplied hardware for the mechanics of some of this system. • Dr G A C Jones who has a high-voltage electron beam lithography tool at the Cavendish Laboratory is collaborating with Dr S. B. Lee in an experimental program to create patterned templates to act as a seeding base for clusters of particles to be assembled out of solution. Arrays of etched pits of various shapes and sizes, of order a few 10s of nanometers have been fabricated on various substrates using the e-beam facility in Cambridge for Dr Lee to investigate cluster formation on these samples. (SBL) • Mr Hongkee Yoon (KAIST student) spent ~8 weeks in the Cavendish working on a new project - 3 Dimensional, grey scale, e-beam lithography. (GACJ) • Dr Jones has been working on other methods of achieving nanostructure fabrication in the “towards 1nm scale”. (GACJ) • 3 dimensional, grey scale, electron-beam Lithography Hongkee Yoon (Kaist) Geb Jones (Cavendish) David Anderson (Cavendish) Motivation • Applications in optical elements: • blazed gratings • sinusoidal, triangular gratings • zone plates • integrated surface lenses for optical interconnects • …….? • Applications in circuit elements • air bridges • MEMs • …….? • Suitable for mass replication using nanoimprint lithography Dose vs resist thickness remaining 2000 0 1 49 97 145 193 241 289 337 385 433 481 529 577 625 673 721 769 817 865 913 - 2000 - 4000 - 6000 - 8000 - 10000 - 12000 • Blue line is measured height (nm) • Red line is calibrated height with max height set as 0 Monte Carlo simulation of 60keV e-beam exposure 1000nm A9 PMMA on Si (Z = 500nm) 1.00E+04 1.00E+03 1.00E+02 1.00E+01 1.00E-02 1.00E-03 1.00E-04 1.00E-05 1.00E-06 1.00E-07 Radius Ri/um 90 80 100 1.00E-01 70 60 50 40 30 20 10 1.00E+00 0 Energy Density per Injected Electron E*/(eV/um^3) 1.00E+05 1000nm A9 PMMA on Si (Z = 500nm) 1.00E+04 1.00E+03 1.00E+02 1.00E+01 1.00E-01 1.00E-02 Radius Ri/um 5 4.5 4 3.5 3 2.5 2 1.5 1 0.5 1.00E+00 0 Energy Density per Injected Electron E*/(eV/um^3) 1.00E+05 Proximity effects in e-beam exposure For double Gaussian approximation to PSF, the energy deposited per electron (normalised to unity in the centre of a large area) is, E ∼ (gα + ηgβ)/(1+η) 1 E= ____ (1+η) Normalised Dose 1 1 __ 2 (1+η) E = ____ =1 (1+η) ( _14 + _14 η) _1 E = _____ = 4 (1+η) 1 _ 1 ( _ + η) 2 2 ______ = _12 E= (1+η) Dose pattern for 3Ghz SAW transducer 3D test pattern with 10 levels of height Calculated dose pattern for 10 x 10 array of 5um square pillars having 10 levels of height. Corner of 10 x 10 pillar array showing corrected doses calculated on 50nm grid Exposed array without proximity correction AFM image (uncorrected array) AFM scan (uncorrected exposure) Proximity corrected 10 by 10 array AFM image (corrected exposure) AFM scan (corrected exposure) Sine wave grating slit pattern Diffraction images from sine wave grating slit diffraction images “Towards 1nm lithography” Sub-10nm, high aspect ratio patterning of ZnO nanostructures using zinc napthenate negative e-beam resist G.A.C. Jones 1, M.S. Saiffullah 1, K. R. V. Subramanian 1, D. Anderson 1, D-J. Kang 2, W.T.S. Huck 1 and M.E. Welland 1. 1 University of Cambridge, U.K. 2 Sungkyunkwan University, Korea. Why direct writing of oxides? ¾Fundamental studies on nanoscale oxide systems Basic transport properties, optoelectronics, nanophotonics, nanoferromagnetism, nanoferroelectricity, etc. ¾To enable patterning of thick or complicated oxide layers Conventional lift-off technique for patterning thick and complicated oxide layers does not work. Use a spin-coatable oxide resist for direct writing to circumvent the problem associated with lift-off technique. It also improves tolerances and reduces processing steps. Resist Preparation Alkoxide Route (TiO2, ZrO2, Al2O3) Naphthenate Route (ZnO) Preparation of spin-coatable oxide resists of TiO2, ZrO2 and Al2O3 Alkoxide: Titanium n-butoxide, Zirconium n-butoxide, Aluminium tri-sec-butoxide Stabilizers: β-diketones and β-ketoesters Solvents: Methanol, Ethanol, Iso-propyl alcohol Glove Box <5% relative humidity alkoxide + stabilizer + solvent Mixing for 2 hours Ratio of alkoxide to stabilizer typically 1:1 Sub-10 nm lines of TiO2 using a Leica VB6-UHR Nanowriter M. S. M. Saifullah, K. R. V. Subramanian, E. Tapley, D-J. Kang, M. E. Welland & M. Butler. Nano Letters, 3, 1587 (2003). Sub-10 nm lines of ZrO2 using a Leica VB6-UHR Nanowriter K. R. V. Subramanian, M. S. M. Saifullah, E. Tapley, D-J. Kang, M. E. Welland & M. Butler. Nanotechnology, 15, 158 (2004). Resist Preparation Alkoxide Route (TiO2, ZrO2, Al2O3) Naphthenate Route (ZnO) What are metal naphthenates? Metal naphthenates consist of cyclopentanes or cyclohexanes, methylene chains [-(CH2)-], carboxylates and metals. They can be represented as: [(cyclopentane) – (CH2)n – COO]–m – Mm+ where M is a metal atom. They are sticky liquids at room temperature and are stable in air. Hence they do not require any special treatment like alkoxides. E-beam damage of zinc naphthenate resist Previous infrared studies suggest that the exposure of naphthenate molecules to an e-beam results in building bridges between them at the –(C=O)– and/or –(CH2)n– groups thereby increasing the molecular weight of the resist. This makes electron-beam exposed naphthenate resists insoluble in toluene. [Kakimi et al, Jpn. J. Appl. Phys., 33, 5301 (1994)] Zinc naphthenate _ H H H H C H C C H O C C O C C H _ H H n H H X-linking occurs here 2+ Zn ditto Process details • Zinc naphthenate (67 wt.-% in mineralised spirits) diluted 1:20 in toluene. • Filter and spin coat @ 4000rpm for 30s • (~90nm thick). • Expose at 30mC.cm-2 using 100kV 1.5nA beam. • Develop in toluene for 10s • Blow dry (no rinse) • Characterise using DI NanoscopeTM AFM and LEO1530VP SEM. E-beam sensitivity of zinc naphthenate resist 1 Normalized Thickness 0.8 0.6 0.4 Sensitivity ~ 15 mC cm Contrast, γ = 3.3 0.2 -2 0 1 10 Electron Dose mC cm 100 1000 -2 Sensitivity at half the normalized thickness is 15 mC cm-2 and the contrast (γ) is 3.3. M. S. M. Saifullah, K. R. V. Subramanian, D-J. Kang, D. Anderson, W. T. S. Huck, G. A. C. Jones & M. E. Welland, Advanced Materials, 17, p. 1757 (2005). Comparative study of sensitivities Resist Sensitivity Type Voltage TiO2 35 mC cm-2 Negative 100 kV ZrO2 40 mC cm-2 Negative 100 kV Al2O3 20 mC cm-2 Negative 100 kV ZnO 15 mC cm-2 Negative 100 kV Calixarene 20 mC cm-2 Negative 70 kV SAL-601 0.07 mC cm-2 Negative 70 kV HSQ 0.7 mC cm-2 Negative 100 kV PMMA 0.6 mC cm-2 Positive 100 kV Sub-10 nm lines of ZnO using a Leica VB6-UHR Nanowriter Sub-10 nm lines of ZnO in the 500 µm main field High aspect ratio structures Aspect Ratio (for narrowest features) > 11 Post Development Bake studies on zinc naphenate resist TGA & DTA studies of zinc naphthenate resist 0 Time, minutes 40 60 20 80 1100 TGA Trace Step 3: -90.37% -9.3 mg 8 Heating rate = 10 C min 6 Step 1: -32.4% -3.34 mg 4 Heat Treatment Temperature = 500 C Z 1000 Starting mass = 10.29 mg -1 900 Step 2: -41.8% -4.3 mg Z Intensity (A. U.) Weight, mg 10 2 0 Z S 800 50 Rate of Mass Loss, mg/min X-ray diffraction data 100 12 150 250 350 450 550 650 Temperature, C 750 850 950 0.2 X 700 0 Z First Derivative Of TGA Trace -0.2 Z Z S 600 X -0.4 -0.6 500 25 -0.8 30 35 40 45 50 55 60 Angle, 2 θ -1 50 150 250 350 450 550 650 750 850 950 Temperature, C Temperature Difference, C 6 4 Heat Treatment at 500°C gives polycrystalline films of ZnO. Z = ZnO, S = Substrate and X = Contamination peaks SDTA Trace 2 0 -2 -4 -6 -8 0 20 40 60 Time, minutes 80 100 65 Optimization of Post Development Bake for photoluminescence in ZnO at 500° 500 C 540 Air Ar Ar + 1% O Ar + 5% H 421 Peaks at 368nm (UV band-edge emission), 421nm (blue emission), 459nm (weak blue emission) and 501nm (green) were observed. 2 2 Normalized Intensity 501 368 459 300 350 400 450 500 550 Wavelength, nm 600 650 700 The presence of slightly broad peaks (368nm and 421nm) and visible range peak (501nm) suggest that the material still has some oxygen vacancies and other defects that cannot be completely removed by this 500°C heat-treatment process. Sub-10nm lines of ZnO using a Leica VB6-UHR Nanowriter Conclusions 9Sub-10 nm, high aspect ratio structures (>10) have been directly fabricated in ZnO by high resolution e- beam lithography using spincoatable, zinc napthenate as a negative resist. 9Exposure to an electron beam makes napthenate based resists insoluble in organic solvents such as toluene. 9The electron beam sensitivity of these materials is comparable to that of conventional electron beam resists such as calixarene and other metallic oxide resists based on metalic alkoxides. 9Post development baking at 500C for 1 hour in an argon/hydrogen ambient drives off the organic component of the resist, shrinking the feature size and drives the formation of the Zn-O bond enhancing the photoluminescence spectrum. 9The line edge roughness of the these patterns ~2.8nm (3σ) pre bake and ~2nm (3σ) post bake is the smallest measured value so far of any e-beam resist.