This document discusses atomic layer deposition (ALD) applications, films, deposition characteristics, and processes. It summarizes that ALD can be used to deposit thin, conformal films for applications in semiconductors, optics, MEMS, and more. ALD works by separating gas precursors and allows for precise, digital thickness control at the atomic scale through self-limiting surface reactions.

1. July 2011 Cambridge NanoTech ALD Tutorial

2. ALD Applications Other applications Roll to rollInternal tube linersNano-glueBiocompatibleMagnetic Chemical CatalysisFuel cells Semi / Nanoelectronics Flexible electronics Gate dielectricsGate electrodesMetal InterconnectsDiffusion barriersDRAMMultilayer-capacitorsRead heads MEMS Etch resistanceHydrophobic / antistiction Optical AntireflectionOptical filtersOLED layersPhotonic crystalsTransparent conductorsElectroluminescenceSolar cellsLasersIntegrated opticsUV blockingColored coatings Nanostructures Inside poresNanotubesAround particlesAFM tips Wear resistant Blade edgesMolds and diesSolid lubricantsAnti corrosion Cambridge NanoTech Inc. Confidential

3. ALD Films - ALD films deposited with digital control of thickness; “built layer-by layer” - Each film has a characteristic growth rate for a particular temperature Common ALD Materials ALD Deposition Rates at 250°C Oxides Al2O3, HfO2, La2O3, SiO2, TiO2, ZnO, ZrO2, Ta2O5, In2O3, SnO2, ITO, FeOx, NiO2, MnOx, Nb2O5, MgO, NiO, Er2O3 Nitrides WN, Hf3N4, Zr3N4, AIN, TiN, TaN, NbNx Metals Ru, Pt, W, Ni, Co Sulphides ZnS 1.26 Å 1.08 Å 0.38 Å Cambridge NanoTech Inc. Confidential

4. Benefits of ALD Perfect films Digital control of film thickness Excellent repeatability 100% film density Amorphous or crystalline films Conformal Coating Excellent 3D conformality Ultra high aspect ratio (>2,000:1) Large area thickness uniformity Atomically flat and smooth coating Challenging Substrates Gentle deposition process for sensitive substrates Low temperature and low stress Excellent adhesion Coats challenging substrates – even teflon Cambridge NanoTech Inc. Confidential

5. ALD Reaction Sequence ALD is based on the spatial separation of precursors A single ALD cycle consists of the following steps: 1) Exposure of the first precursor 2) Purge or evacuation of the reaction chamber to remove the non-reacted precursors and the gaseous reaction by-products 3) Exposure of the second precursor – or another treatment to activate the surface again for the reaction of the first precursor 4) Purge or evacuation of the reaction chamber Single Cycle Precursor A Purge Precursor B Purge Time Cambridge NanoTech Inc. Confidential

6. ALD Example Cycle for Al2O3 Deposition Tri-methyl aluminum Al(CH3)3(g) Methyl group (CH3) Al H C H H H O Substrate surface (e.g. Si) In air H2O vapor is adsorbed on most surfaces, forming a hydroxyl group. With silicon this forms: Si-O-H (s) After placing the substrate in the reactor, Trimethyl Aluminum (TMA) is pulsed into the reaction chamber. Cambridge NanoTech Inc. Confidential

7. Methane reaction product CH4 H Reaction of TMA with OH H C H H H H C C H H H Al O Substrate surface (e.g. Si) Al(CH3)3 (g) + : Si-O-H (s) :Si-O-Al(CH3)2(s) + CH4 ALD Cycle for Al2O3 Trimethylaluminum(TMA) reacts with the adsorbed hydroxyl groups, producing methane as the reaction product Cambridge NanoTech Inc. Confidential

8. ALD Cycle for Al2O3 Methane reaction product CH4 Excess TMA H H C C H H Al O Substrate surface (e.g. Si) Trimethyl Aluminum (TMA) reacts with the adsorbed hydroxyl groups, until the surface is passivated. TMA does not react with itself, terminating the reaction to one layer. This causes the perfect uniformity of ALD. The excess TMA is pumped away with the methane reaction product. Cambridge NanoTech Inc. Confidential

9. ALD Cycle for Al2O3 H2O O H H H H C C H H Al O After the TMA and methane reaction product is pumped away, water vapor (H2O) is pulsed into the reaction chamber. Cambridge NanoTech Inc. Confidential

10. 2 H2O (g) + :Si-O-Al(CH3)2(s) :Si-O-Al(OH)2(s) + 2 CH4 ALD Cycle for Al2O3 Methane reaction product New hydroxyl group Methane reaction product Oxygen bridges H O O Al Al Al O H2O reacts with the dangling methyl groups on the new surface forming aluminum-oxygen (Al-O) bridges and hydroxyl surface groups, waiting for a new TMA pulse. Again metane is the reaction product. Cambridge NanoTech Inc. Confidential

11. ALD Cycle for Al2O3 H O O O Al Al Al O The reaction product methane is pumped away. Excess H2O vapor does not react with the hydroxyl surface groups, again causing perfect passivation to one atomic layer. Cambridge NanoTech Inc. Confidential

12. H H H O O O O O Al Al Al O O O O O Al Al Al O O O O O Al Al Al O O O Al(CH3)3 (g) + :Al-O-H (s) :Al-O-Al(CH3)2(s) + CH4 ALD Cycle for Al2O3 One TMA and one H2O vapor pulse form one cycle. Here three cycles are shown, with approximately 1 Angstrom per cycle. Two reaction steps in each cycle: 2 H2O (g) + :O-Al(CH3)2(s) :Al-O-Al(OH)2(s) + 2 CH4 Cambridge NanoTech Inc. Confidential

13. ALD Deposition Characteristics ALD is insensitive to dose after saturation is achieved Deposition rate remains unchanged with increasing dose MgO Saturation Curve at 250°C Linear MgO Deposition Cambridge NanoTech Inc. Confidential

15. Process parameters inside the ALD window allowfor reliable and repeatable results

16. The ALD window is defined by the precursor volatility / stabilityDecomposition limited Condensation limited Growth Rate Å/cycle ALD Window Saturation Level Temperature Desorption limited Activation energy limited Cambridge NanoTech Inc. Confidential

17. ALD Reaction Temperatures ALD is a chemistry driven process Based on precursor volatility/reactivity Most ALD Processes Reactor Temp >400°C 250°C 300°C 150°C 150°C Room T 200°C 100°C 350°C High precursor volatility, lower thermal stability of precursors Lower precursor volatility, Slow desorption of precursors Cambridge NanoTech Inc. Confidential

18. High Aspect Ratio Coatings ALD is uniquely suited to coat ultrahigh aspect ratio structures enabling precise control of the coatings thickness and composition. Cambridge NanoTech’s research systems offer deposition modes for ultra high aspect ratio (>2,000:1) “Capillary tube” Cross Sectional SEM AAO template* *Image courtesy of the University of Maryland Cambridge NanoTech Inc. Confidential

19. Compositional Uniformity Refractive Index – Ellipsometry Cross sectional EDX 2.104 2.103 2.101 2.101 2.105 2.102 2.104 2.104 2.101 2.103 2.103 2.103 2.099 2.101 2.104 Al2O3 Silica aerogel foam Ta2O5 - 500Å film Cambridge NanoTech Inc. Confidential

20. ALD Precursors Good ALD precursors need to have the following characteristics: Volatility Vapor pressure (> 0.1Torr at T < 200°C) without decomposition Stability No thermal decomposition in the reactor or on the substrate Reactivity Able to quickly react with substrate in a self-limiting fashion (most precursors are air-sensitive) Byproducts Should not etch growing film and/or compete for surface sites Availability Precursor cylinders Cambridge NanoTech Inc. Confidential

22. Expands ALD window for materials by decreasing activation energy

23. Lower temperature possible: avoids precursor decomposition

24. Faster deposition cycle times

25. Fewer contaminates in filmsSingle Cycle Fiji PE-ALD chamber Precursor A Purge Plasma On Plasma Purge Time Cambridge NanoTech Inc. Confidential

26. Plasma Enhanced (PE)ALD Plasma ALD processes are used for a variety of oxides, nitrides, and metals, including titanium nitride, platinum, and other materials, allowing for low resistivity of titanium nitride, and significantly lower temperatures for depositing platinum. Cambridge NanoTech Fiji Manifold Cambridge NanoTech Fiji Chamber Cambridge NanoTech Inc. Confidential

28. Low Temperature ALD Some ALD processes can deposit films < 150°C: Al2O3, HfO2, SiO2, TiO2, ZnO, ZrO2, Ta2O5, SnO2, Nb2O5, MgO Ideal for merging organics with inorganics Compatible with photoresist, plastics, biomaterials Cambridge NanoTech Inc. Confidential

29. Product Portfolio Cambridge NanoTech ALD systems are engineered for a wide variety of applications from research to high-volume manufacturing. These systems deposit precise, conformal and ultra-thin films on multiple substrates. Their simplified system designs yield low startup and operating costs. Savannah Fiji Phoenix Tahiti Compact, cost-effective system for research Plasma system for research Batch manufacturing system Large area manufacturing system Production Research Cambridge NanoTech Inc. Confidential