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23-May-17 1 Overview Introduction Principle Precursor Requirements Process Comparison to CVD Process Applications Advantages and Disadvantages ALD Tool in NNfC - CeNSE 23-May-17 2 • Atomic layer deposition (ALD) is a chemical vapour deposition technique based on the sequential self terminating gas-solid reactions to give thin films of nanometer range. • ALD reactions use two chemical sources, A and B of as shown in Figure. 1, typically called precursors1. • These precursors react with a surface one at a time in a sequential, self-limiting2 manner. • By exposing the precursors to the growth surface repeatedly, a thin film is deposited as per required thickness. • Atomic layer growth can be obtained as 1 Å per cycle and Atomic layer can be controlled upto ῀0.1 Å (10 pm3) per cycle • ALD can be used to deposit several types of thin films, including various metal oxides (e.g. Al2O3, TiO2, SnO2, ZnO, HfO2), metal nitrides (e.g. TiN, TaN, WN, NbN), metals (e.g. Ru, Ir, Pt), and metal sulfides (e.g. ZnS). Definition: 1 One of the compounds that participates in the chemical reaction that produces another compound 2 The amount of film material deposited in each reaction cycle is constant 3 1pm ( picometer) = 1x10-12 23-May-17 3 • Atomic layer deposition principle was first published under the name “Molecular Layering” (ML) in the early 1960s by Prof. S.I. Kol’tsov from the Leningrad (Lensovet) Technological Institute (LTI), Russia • Introduced in 1974 by Dr. Tuomo Suntola and co-workers in Finland to improve the quality of ZnS films used in electroluminescent displays • Recently, it turned out that ALD method also produces outstanding dielectric layers and attracted semiconductor industries for making High-K dielectric materials. 23-May-17 4 Principle of ALD Technique: [Per Cycle] • • • First precursor gas (A Source) is introduced into the process chamber and produces a monolayer on the wafer surface. Then a second precursor gas (B Source) is introduced into the chamber, which reacts with the first precursor to produce a monolayer of film on the wafer surface. Separation of the precursors is accomplished by pulsing a purge gas (typically nitrogen or argon) after each precursor pulse to remove excess precursor from the process chamber and prevent 'parasitic' CVD deposition on the substrate. Two fundamental mechanisms: Chemisorption saturation process Sequential surface chemical reaction process Example: ALD cycle for Al2O3 deposition A Source : H2O ; B Source: Tri methyl Aluminum (TMA) Four stages of one ALD cycle: 1. Exposure of substrate to precursor A : Absorption 2. Purge with N2 or Ar : Removal of excess precursor A 3. Exposure of substrate with precursor B :R e a c t i o n 4. Purge with N2 or Ar : R e m o v a l of excess precursor B and reaction products 23-May-17 Figure. 1 5 Good ALD precursors need to have the following behaviours: Volatile Vapour pressure ( > 0.1Torr at T < 200°C ) Liquid at volatilization temperature without decomposition Reactive Able to quickly react with substrate in a self-limiting fashion (most precursors are air-sensitive) Stable Thermal decomposition in the reactor or on the substrate is not allowed By products Should not etch growing film and/or compete for surface sites B Source A Source Available The second precursor (B Source) must react with adsorbed monolayer (A Source) in order to form bonds and prepare the surface for another dose of (A Source) Some common precursors include: Oxidants – for Oxides Water (H2O), Ozone, Alcohols (ROH), Metal Alkoxides [M(OR)x] Reductants Metals Hydrogen gas (H2), Ammonia (NH3), Silanes (Si2H6) Nitrides Ammonia (NH3), Hydrazine (NH2-NH2) Sulfides Hydrogen Sulfide (H2S) 23-May-17 6 Closed System Chamber( Most Common) 23-May-17 Process Temperature Step Coverage & Deposition Rate Vs. Deposition Technique 7 Per Cycle One Cycle Acceptable temperature range for deposition. 23-May-17 Process Temperature 8 Process: Step 1a 23-May-17 9 Step 1b 23-May-17 10 Step 1c 23-May-17 11 Step 2a 23-May-17 12 Step 2b 23-May-17 13 Step 2c 23-May-17 14 After 3 Cycles 23-May-17 15 ALD CVD Highly Reactive Precursors Less Reactive Precursors Precursors react separately on the Precursors react at the same time on the substrate Precursors must not decompose at Precursors can decompose at process temperature substrate process temperature Uniformity ensured by the saturation mechanism Thickness control by counting the number of reaction cycles Surplus precursor dosing acceptable 23-May-17 Uniformity requires uniform flux of reactant and temperature Thickness control by precise process control and monitoring Precursor dosing important 16 MBE: Molecular Beam Epitaxy ; CVD: Chemical Vapour Deposition ; PLD: Plasma Layer Deposition 23-May-17 17 23-May-17 18 23-May-17 19 23-May-17 20 23-May-17 21 23-May-17 22 23-May-17 23 23-May-17 24 Doping in ALD..!!!! Doping is carried out by substituting a pulse of precursor A with dopant precursor B This allows exploration of a wide concentration window without having to prepare new targets for each concentration (as in sputtered depositions) Substrate Dopant cycle B Grated films with uniform properties possible Annealing films to “activate” dopants is not required 23-May-17 25 High-K dielectrics for CMOS: • • • Reduces Leakage Current Faster Switching Speed Cooler Transistors Candidates for High-K dielectrics Film Precursors Al2O3 Al(CH)3, H2O or O3 HfO2 HfCl4 or TEMAH, H2O ZrO2 ZrCl4, H2O Semiconductor memory (DRAM) ZnO Si Cu interconnect barrier Deposition in porous structures Very good at coating non planar surfaces (On Si High Aspect Ratio Trenches) Mixed Oxide Deposition: Layer by Layer 23-May-17 26 Advantages of ALD: Uniformity Conformal Step Coverage High Density Film and No Pinholes Precise Thickness Control of Deposited Films Gentle Deposition Process for Sensitive Substrates Disadvantages of ALD: Deposition Rate Slower than CVD Expensive Equipment Critical adjustment of the flow: Too much flow => Clogging of valves Too low flow => Under-performance 23-May-17 27 Technical Specification: Manufacturer: Beneq Model: TFS 200 No. of Tool : 1 Year of Manufacture: 2009 Place of Manufacture: Vantaa, Finland Tool Installed : 2010, CeNSE, IISc - Bangalore 23-May-17 Substrate temperature range: 25 - 500 °C Reaction chamber types and dimensions: Single wafer: Ø 200 × 3 (mm) Gas lines: up to 8 Liquid sources (+5 °C to ambient): up to 4 Hot source HS 300 (ambient to 300 °C): up to 4 Hot source HS 500 (ambient to 500 °C): up to 2 Plasma specifications (PEALD) Power: 300 W Type: Capacitive Coupled Plasma (CCP) Fluidized bed particle coating option: - particle size (min.) : 100 nm - 1 μm - sample volume (max.) : 50 - 75 cm3 - temperature (max.): 450 °C Control system: PLC control with PC user interface 28 23-May-17 29