1. Bulk micromachining  Explain the differences between isotropic and anisotropic etching  Explain the differences between wet and dry etching techniques  Identify several common wet etchants and explain what they are commonly used for  Explain the difference between rate limited and diffusion limited reactions  Explain in general terms the different theories behind the differences in etch rate for different crystal directions in the anisotropic etching of silicon  Discern the resulting shapes of trenches (pits) resulting from the anisotropic etching of Si for different mask and wafer combinations  List and explain the most common etch stop techniques  List and describe the most common dry etching techniques  Perform basic calculations for wet etching processes

2. Bulk micromachining Silicon wafer Silicon etched SiO 2 Isotropic etch Anisotropic etch

3. Etching Chemical reaction resulting in the removal of material Etching: Wet etching: Dry etching: etchants in liquid form etchants contained is gas or plasma ionized gas Etch rate:material removed per time (μm/min)

4. Selectivity and undercutting etch rate of one material compared to another Selectivity: Undercutting etch rate of one crystalline direction compared to another [100][111] SEM image of a SiO 2 cantilever formed by undercutting (S. Mohana Sundaram and A. Ghosh, Department of Physics, Indian Institute of Science, Bangalore) SiO 2 (100) Si 54.7°

5. Application and properties of different wet etchants High HF tends to etch SiO 2 Acidic etchants tend to etch Si isotropically Basic etchants tend to etch Si anisotropically Depend on concentration and temperature

6. Rate versus diffusion limited etching Etchant Products Etchant Products Rate limited reaction Diffusion limited reaction Rate limited reactions are preferred  easier to control and more repeatable

7. Isotropic etching Estimate of etch depth depth ≈ (D-d)/2 Etch rate is the same in all directions Typically acidic Room temperature Isotropy is due to the fast chemical reactions X μm/min to XX μm/min  Reaction or diffusion limited? D d undercutting

8. Isotropic etching HNA: HF/HNO 3 /HC 2 H 3 O 2 Used in isotropic etching of silicon Also called poly etch HNO 3 (aq) + Si(s) + 6HF (aq)  H 2 SiF 6 (aq) + HNO 2 (aq) + H 2 O (l) + H 2 (g) The etching process actually occurs in several steps. First step, nitric acid oxidizes the silicon HNO 3 (aq) + H 2 O (l) + Si (s)  SiO 2 (s) + HNO 2 (aq)+ H 2 (g) In the second step, the newly formed silicon dioxide is etched by the hydrofluoric acid. SiO 2 (s) + 6HF (aq)  H 2 SiF 6 (aq) + 2 H 2 O (l)

9. Isotropic etching BOE (Buffered Oxide Etch): HF/NH 4 F/H 2 O Used in isotropic etching of silicon dioxide and glass Basically proceeds from the second step of etching Si: SiO 2 (s) + 6HF (aq)  H 2 SiF 6 (aq) + 2 H 2 O (l)

10. Anisotropic etching Etch depths depend on geometry Undercutting also depends on geometry Etch rate is different for different crystal plane directions Typically basic etchants Elevated temperatures (70-120°C) Different theories propose for anisotropy Slower etch rates, ~ 1 μm/min  Reaction or diffusion limited? d undercutting [100] [111] 54.7°

11. Properties of different anisotropic etchants of Si

12. Theories for anisotropic etching Siedel et al. The lower reaction rate for the {111} planes is caused by the larger activation energy required to break bonds behind the etch plane. This is due to the larger bond density of silicon atoms behind the {111} plane. Silicon lattice (100) (111) 2 dangling bonds 1 dangling bond

13. Theories for anisotropic etching Siedel et al. (Continued) Reduction of water believed to be the rate determining step OH - believed to be provided by H 2 O near Si surface Si + 2OH -  SiOH 2 ++ + 4 e - (oxidation step) SiOH 2 ++ + 4 e - + 4 H 2 O  Si(OH) 6 -- +2 H 2 (reduction step) Elwenspoek et al. Suggests surface roughness is reason {111} plane is atomically flat, no nucleation sites

14. Self-limiting etch and undercutting D [111] D Intersection of {111} planes can cause self-limiting etch. Only works with concave corners Concave corner Convex corner exposes other planes Resulting undercutting can be used to create suspended structures

15. Anisotropic etching of (110) silicon {110} {111} Top view Long narrow mask openings can be used to create long narrow channels with vertical sidewalls Mask with small aspect ratio Mask with large aspect ratio {110} planes etch about twice as fast as {100} planes in KOH Vertical sidewalls and 90° angles!

16. Anisotropic etching of (111) silicon How fast does the (111) plane etch? pre-etched pit protected sidewalls  usually used as base (Big green Lego®) for surface micromachining Sin embargo, todavía es posbile usar lo en “bulk micromachining”

17. Te toca a ti Sketch the cross-sections resulting from anisotropically etching the silicon wafers shown with the given masks.

18. Etch stop Etch stop:Technique to actively stop the etching process Insulator etch stop Self-limiting etch Timed etch Etch stop via doping p-n junction insulting layer

19. Etch stop via doping Boron etch stop n type wafer heavily doped with B (called a p+ wafer) p-n junction Si + 2OH -  SiOH 2 ++ + 4 e - (oxidation step) SiOH 2 ++ + 4 e - + 4 H 2 O  Si(OH) 6 -- +2 H 2 (reduction step) High level of p-type doping is not compatible with CMOS standards for integrated circuit fabrication p region Si deficient in e - n region p region

20. Etch stop via doping Electrochemical etch stop (ECE) Very light doping compared to boron etch stop. OK with CMOS standards for integrated circuit fabrication. p type wafer doped n-type dopant p-n junction “Reverse bias” voltage applied to p-n junction keeps current from flowing n region p region Si + 2OH -  SiOH 2 ++ + 4 e - (oxidation step) SiOH 2 ++ + 4 e - + 4 H 2 O  Si(OH) 6 -- +2 H 2 (reduction step) diode -V+-V+ e-e- e-e- SiO 2

21. Dry etching Chemical reaction resulting in the removal of material Etching: Wet etching: Dry etching: etchants in liquid form etchants contained is gas or plasma Plasma etching: Chemically reactive gas formed by collision of molecules of reactive gas with energetic electrons Excited/ignited be RF (radio frequency) electric field ~ 10-15 MHz Accelerated to target via the electric field Reactive ion etching (RIE): mostly chemical etching In addition to the chemical etching, accelerated ions also physically etch the surface + + + + electrodes wafer - - - - - - - - - excited ions

22. Reactive ion etching Plasma hits surface with large energy In addition to the chemical reaction, there is physical etching (Parece tirar piedras en la arena) Can be very directional—can create tall, skinny channels (Intellisense Corporation) If there is no chemical reaction at all, the technique is called ion milling.

23. Common dry etchant/material combinations Material Reactive gas Silicon (Crystalline or polysilicon) Chlorine-base: Cl 2, CCl 2, F 2 Fluorine-base: XeF 2, CF 4, SF 6, NF 3 SiO 2 Fluorine-base: CF 4, SF 6, NF 3 Al Chlorine-base: Cl 2, CCl 4, SiCl 4, BCl 3 Si 3 N 4 Fluorine-base: CF 4, SF 6, NF 3 Photoresist O 2 (Ashing)

24. Deep reactive ion etching (DRIE) Bosch process 1 st, reactive ion etching step takes place 2 nd, fluorocarbon polymer deposited to protect sidewalls Kane Miller, Mingxiao Li, Kevin M Walsh and Xiao-An Fu, The effects of DRIE operational parameters on vertically aligned micropillar arrays, Journal of Micromechanics and Microengineering, 23 (3) “Scalloping”

25. Te toca a ti Wet etching problems 1.A pattern is etched into a Si wafer as described below. Answer the questions that follow. A 300 nm thick layer of oxide is grown on the surface of the Si wafer. Photoresist is applied to the oxide surface, and patterned using standard photolithographic techniques. The pattern is etched into the oxide. The exposed Si is etched anisotropically to achieve the desired feature. a.Should the photoresist be removed before the Si etching step? Justify your answer. b.What etchant will you use for the oxide? c.What etchant will you use for the Si? 2. You are asked to make a V-shaped grooves 60 μm deep in an oxidized silicon wafer a.How wide must the opening in the oxide mask be in order to achieve this result? b.Will the degree of undercutting, due to etching into the plane, be appreciable compared to the dimensions of the desired feature? Justify your answer.