VI. Pattern Transfer: Additive techniques-physical Vapor Deposition and Chemical Vapor Deposition

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1 VI. Pattern Transfer: Additive techniques-physical Vapor Deposition and Chemical Vapor Deposition

2 Content Physical vapor deposition (PVD) Chemical vapor deposition (CVD) Thermal evaporation Reaction mechanisms Sputtering Step coverage Evaporation and sputtering compared MBE CVD overview Epitaxy Laser sputtering Ion Plating Cluster-Beam

3 Physical vapor deposition (PVD) The physical vapor deposition technique is based on the formation of vapor of the material to be deposited as a thin film. The material in solid form is either heated until evaporation (thermal evaporation) or sputtered by ions (sputtering). In the last case, ions are generated by a plasma discharge usually within an inert gas (argon). It is also possible to bombard the sample with an ion beam from an external ion source. This allows to vary the energy and intensity of ions reaching the target surface.

4 Physical vapor deposition (PVD)

5 Physical vapor deposition (PVD): thermal evaporation N = N o exp- e kt The number of molecules leaving a unit area of evaporant per second Heat S ources Advantages Dis advantages Resistance No radiation Contamination e-beam Low contamination Radiation RF No radiation Contamination Laser No radiation, low contamination Expensive 6

6 Physical vapor deposition (PVD): thermal evaporation

7 Physical vapor deposition (PVD): thermal evaporation N (molecules/unit area/unit time) = P v (T)/ (MT) 1/2 This is the relation between vapor pressure of the evaporant and the evaporation rate. If a high vacuum is established, most molecules/atoms will reach the substrate without intervening collisions. Atoms and molecules flow through the orifice in a single straight track,or we have free molecular flow : K n = /D > 1 The fraction of particles scattered by collisions with atoms of residual gas is proportional to: 1-exp (+d/) The source-to-wafer distance must be smaller than the mean free path (e.g, 25 to 70 cm) The cosine law A ~ cos cos /d 2 A: Arrival rate at distance d

8 Physical vapor deposition (PVD): thermal evaporation From kinetic theory the mean free path relates to the total pressure as: = (RT/2M) 1/2 /P T Since the thickness of the deposited film, t, is proportional To the cos, the ratio of the film thickness shown in the Figure on the right with = 0 is given as: t 1 /t 2 =cos /cos How to avoide cracking at the extreme ends of the interval: Heating of substrate during deposition to ºC---increase surface mobility of the metal atoms. Rotating the wafers ---ß varies during deposition.

9 Physical vapor deposition (PVD): sputtering W= kv i P T d Momentum transfer ev -W, the amount of material sputtered from the cathode -V, working voltage - I, discharge current - d, anode-cathode distance - P T, gas pressure - k, proportionality constant The target, at a high negative potential, is bombarded with positive argon ions (or other inert gases) created in a plasma. The target materials is sputtered away mainly as a neutral atoms by momentum transfer and ejected surface atoms are deposited onto the substrate placed on the anode.

10 Physical vapor deposition (PVD): sputtering Sputter yields of commonly used materials with 500eV Argon: Al: 1.05 Cr: 1.18 Au: 2.4 Ni: 1.33 Pt: 1.4 Ti: 0.51 Ion energies: 0.5-3KV are typically used for sputter deposition, as nuclear collisions are predominant in this range. The sputter yields : atoms per ion. >1MeV: deep ion implantation

11 Evaporation and sputtering: comparison Rate Evaporation Thousand atomic layers per second (e.g. 0.5 µm/min for Al) S puttering One atomic layer per second Choice of materials Limited Almost unlimited Purity Better (no gas inclusions, very high vacuum) Possibility of incorporating impurities (low-medium vacuum range) Subs trate heating Very low Unless magnetron is used substrate heating can be substantial Surface damage Very low, with e-beam x-ray damage is possible Ionic bombardment damage In-situ cleaning Not an option Easily done with a sputter etch Alloy compositions, stochiometry Little or no control X-ray damage Only with e-beam evaporation Radiation and particle damage is possible Changes in source Easy Alloy composition can be tightly controlled Expensive material Decompos ition of material High Low Scaling-up Difficult Good Uniformity Difficult Easy over large areas Capital Equipment Low cost More expensive Number of Only one deposition per charge Many depositions can be carried out per target depos itions Thickness control Not easy to control Several controls possible Adhesion Often poor Excellent Shadow ing effect Large Small Film properties (e. g. grain size and step coverage) Difficult to control Control by bias, pressure, substrate heat

12 Physical vapor deposition (PVD): MBE - MBE (Molecular beam epitaxy ) Epitaxy: homo-epitaxy (Si on Si, GaAs on GaAs); hetero-epitaxy (Si on SiO2, GaP on GaAs) Very slow: 1µm/hr (1 monolayer per second) Very low pressure: Torr RHEED (Reflection High Energy Electron Diffraction) is often used for monitoring the growth of the crystal layers. Heated single crystal sample ( ºC) is placed in an ultrahigh vacuum in the path of streams of atoms from heated cells that contain the materials of interest.

13 Physical vapor deposition (PVD): Laser Ablation Traditional Laser ablation with additional laser for surface heating -induce correct crystalline structure - Laser sputter deposition Use intense laser radiation to erode a target and deposit the eroded materials onto a substrate. High energy excimer laser pulse. For example, KrF laser at 248nm with a pulse energy 2J/cm 2 Complex compounds (e.g. HTSC, biocompatible ceramics) Normally, the laser deposited films are amorphous Small source size, not useful for large-scale coatings

14 Physical vapor deposition (PVD): Ion cluster plating Ionized cluster: it is possible to ionize atom clusters that are being evaporated leading to a higher energy and a film with better properties (adherence, density, etc.). From 100 mbar (heater cell) to 10-5 to 10-7 mbar (vacuum)-- sudden cooling Deposits nanoparticles ionized atom clusters: atoms Combines evaporation with a plasma or electron filament» faster than sputtering» complex compositions» good adhesion

15 Physical vapor deposition (PVD):Ion cluster plating and ion plating Gas cluster ions consist of many atoms or molecules weakly bound to each other and sharing a common electrical charge. As in the case of monomer ions, beams of cluster ions can propagate under vacuum and the energies of the ions can be controlled using acceleration voltages. A cluster ion has much larger mass and momentum with lower energy per atom than a monomer ion carrying the same total energy. Upon impact on solid surfaces, cluster ions depart all their energy to an extremely shallow region of the surface. Sputtered material is forced sideways and produces highly lateral sputtering yields. These sputtering properties are unique to gas cluster ions and produce smoother surfaces. Also individual atoms can be ionized and lead to ion plating (see figure on the right, example coating : very hard TiN)

16 Chemical Vapor Deposition Model UHV-CVD-5000 (tekvac.com) AX kW Integration (ASTeX) hot filament chemical vapor deposition (HFCVD) system (Argonne National Lab) Very versatile: Amorphous, polycrystalline, epitaxial, single crystalline

17 Chemical vapor deposition (CVD): reaction mechanisms Mass transport of the reactant in the bulk Gas-phase reactions (homogeneous) Mass transport to the surface Adsorption on the surface Surface reactions (heterogeneous) Surface migration Incorporation of film constituents, island formation Desorption of by-products Mass transport of by-produccts in bulk CVD: Diffusive-convective transport of depositing species to a substrate with many intermolecular collisions-driven by a concentration gradient Si SiH4 SiH 4

18 Chemical vapor deposition (CVD): reaction mechanisms Energy sources for deposition: Thermal Plasma Laser Photons Deposition rate or film growth rate Fl = D c x 1 2 (x) x U (Fick s first law) (Boundary layer thickness) (U) Laminar flow L dx (x) (gas viscosity, gas density, gas stream velocity U) 1 L L (x)dx 2 L 3 UL (Dimensionless Reynolds number) Re L UL Fl = D c 2L 3 Re L (by substitution in Fick s first law and x=) = 2L 3 Re L

19 Chemical vapor deposition (CVD) : reaction mechanisms Surface reaction can be modeled by a thermally activated phenomenon proceeding at a rate, R. For a certain rate-limiting reaction, T may rise high enough for the reaction rate to exceed the rate at which reactant species arrive at the surface. In such a case, the reaction rate can t proceed any faster than the rate at which the reactant gases are supplied to the substrate by mass transport, no matter how high the temperature is raised. This situation is referred to as a masstransport-limited deposition process. T is less important in this regime than it is in the reaction-rate limited one. Fl = D c 2L 3 Re L R = R o e - E a kt

20 LPCVD for Si Technology

21 Mass Flow Limited Regime vs. Reaction Rate Limited Regime Application: Mass flow controlled regime (square root of gas velocity) (e.g. AP CVD~ kpa) : all wafers are supplied with an equal flux of reactant species. (Faster) Thermally activated regime: rate limiting step is surface reactionarrival rate is less important LP CVD ~ 1Torr---D is very large, x1000 higher than APCVD (Slower) R = R o e - E a kt Fl = D c 2L 3 Re L

22 Chemical vapor deposition (CVD): step coverage Step coverage, two factors are important Mean free path and surface migration i.e. P and T Mean free path: kt 1 a 2 2 P T a 2 a z w arctan w z 80 0 is angle of arrival

23 Chemical vapor deposition (CVD) : overview CVD (thermal) APCVD (atmospheric) LPCVD (<10 Pa) VLPCVD (<1.3 Pa) UHVCVD (10-7 Pa) PE CVD (plasma enhanced) MPCVD (microwave plasma-cvd) Photon-assisted CVD Laser-assisted CVD MOCVD CVD diamond

24 Chemical vapor deposition (CVD) : L-CVD The LCVD method is able to fabricate continuous thin rods and fibres by pulling the substrate away from the stationary laser focus at the linear growth speed of the material while keeping the laser focus on the rod tip, as shown in the Figure. LCVD was first demonstrated for carbon and silicon rods. However, fibres were able to grown from hundreds of substrates including silicon, carbon, boron, oxides, nitrides, carbides, borides, and metals such as aluminium. The LCVD process can operate at low and high chamber pressures. The growth rate is normally less than 100 µm/s at low chamber pressure (<<1 bar). At high chamber pressure (>1 bar), high growth rate (>1.1 mm/s) has been achieved for smalldiameter (< 20 µm) amorphous boron fibres.

25 Epitaxy VPE: MBE (PVD) (see above) MOCVD (CVD) i.e.organo-metallic CVD(e.g. trimethyl aluminum to deposit Al) (see above) Liquid phase epitaxy Solid epitaxy: recrystallization of amorphous material (e.g. poly-si) Liquid phase epitaxy

26 Epitaxy Selective epitaxy Epi-layer thickness: IR Capacitance,Voltage Profilometry Tapered groove Angle-lap and stain Weighing Selective epitaxy

27 Other methods Silk-screening or screen printing The lithographic pattern in the screen emulsion is transferred to a substrate by forcing the paste through the mask openings with a squeeze. Sol-gel deposition Plasma spraying Typical particle (100micron) deposition methods Others: dip-pen, glow discharge polymerization, electroplating.

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