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Wet Etch

1) Etching is commonly used to pattern materials and is usually done through a mask. Soft masks like photoresist and hard masks like SiOx and Si3N4 are used. 2) Key parameters for etching include etch rate, selectivity, anisotropy, and bias. High selectivity and anisotropy are preferred. 3) Wet etching uses chemical solutions and is isotropic while dry etching uses plasma and is anisotropic. Both have advantages and disadvantages. 4) Common etchants and their recipes are described for various materials like SiO2, Si3N4, metals, and III-V semiconductors. Anisotropic wet etching of silicon

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370 views28 pages

Wet Etch

1) Etching is commonly used to pattern materials and is usually done through a mask. Soft masks like photoresist and hard masks like SiOx and Si3N4 are used. 2) Key parameters for etching include etch rate, selectivity, anisotropy, and bias. High selectivity and anisotropy are preferred. 3) Wet etching uses chemical solutions and is isotropic while dry etching uses plasma and is anisotropic. Both have advantages and disadvantages. 4) Common etchants and their recipes are described for various materials like SiO2, Si3N4, metals, and III-V semiconductors. Anisotropic wet etching of silicon

Uploaded by

khalil alhatab
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Etching mask

Etching usually done through a mask of

Soft mask Hard mask


Photoresist SiOx, Si3N4, Cr

PR
Hard Material
PR

PR strip

(photoresist to define hard mask)


More robust than PR alone
Characterization of etching

1) Etch rate (Å/min)

2) Selectivity
etch rate of A
S
etch rate of B

High selectivity is preferred

3) Anisotropy
Lateral Etch Rate
A  1
Vertical Etch Rate

Undercut
4) Bias
Etching

Wet etching Dry etching


- by wet chemical solution
- by plasma
- Isotropic etching
- Anisotropic etching

Vertical E/R = Horizontal E/R Vertical E/R  Horizontal E/R


Pure chemical reaction Ion assisted
High selectivity Relatively low selectivity
CD loss No CD bias
Directionality of Etching Processes

A=0 Anisotropic, A = 1
Key ingredients in any wet etchant

- Oxidizer
examples: H2O2, HNO3
- Acid or base to dissolve oxidized surface
examples: H2SO4, NH4OH, HF
- Dilution media to transport reactants and products through
examples: H2O, CH3COOH

 Wet etch processes are generally isotropic


 Wet etch processes can be highly selective
 Acids are commonly used for etching
Advantage and disadvantage

• Advantages
- high selectivity
- Easy process

• Disadvantages
- Contamination from the solution
- Difficulty in controlling the process
(temperature and concentration dependent)
- Isotropic etching
- Resist scumming
- Not fit for less 2 m features
- bubble formation at the interface blocks the direct contact of etchant
to the substrate surface

Imcomplete development
SiO2 etching

Etchant : HF (6) : H2O (1)

SiO2  6 HF  H 2  SiF6  2 H 2O

Selectivity over polysilicon = 100

Buffering agent : NH4F

The concentration HF decreases with


reaction  etch rate decreases

Add buffering agent to keep the rate


NH 4 F  NH 3  HF

Native silicon oxide can be easily removed with much diluted HF solution
Substrate surface: hydrophilic to hydrophobic
Silicon etching

1) Isotropic etching
Use HF + HNO3 + H2O (or CH3COOH)
• Step 1: Oxidation
Si + 4HNO3  SiO2 + 2H2O + 4NO2
• Step 2: Oxide dissolution
SiO2 + 6HF  H2 + SiF6 + 2H2O

1 region: For high HF, contours are parallel to the lines of constant HNO 3
 Controlled by HNO3 concentration
2 region: For high HNO3, contours are parallel to the lines of constant HF
 Controlled by HF concentration
3 region: the etch rate falls for 1:1 HF:HNO 3 ratio as with the dilution
Si3N4 etching
6 parts 40% NH4F and 1 part 49% HF
• Silicon Nitride is etched very slowly
in 20:1 BOE solution at 20oC
- Etch rate of SiO2 : 300 Å/min
- Etch rate of Si3N4 : 5 ~ 15 Å/min
- Very good selectivity of oxide to nitride

• Phosphoric acid at 150oC


etches Si3N4 at fairly fast rate
- Etch rate of Si3N4 : 100 Å/min
- Etch rate of SiO2 : 10 Å/min
- Selectivity of Si3N4 over SiO2 : S = 10
- Selectivity of Si3N4 over Si : S = 30
Metal etching
Aluminum
- “Metal etch” (3:3:1:1 H3PO4:HNO3:CH3COOH:H2O)
20 min/m @RT, 4min/m @ 40oC

Chromium – usually requires depassivation


(1) Cyantek CR-7s (perchloric based, 7min/m)
(2) 1:1 HCl : Glycerin (12 min/m)

Gold (Au) and Platinum (Pt)


- Aqua Regia (3:1 HCl : HNO3, 1.5 sec/m)

Copper (Cu)
- 150g Sodium persulfate: 1000ml H2O, ~ 20sec/m)

Silver (Ag)
- “dilute metal etch” (3:3:23:1 H PO :HNO :CH COOH:H O), 10min/100Å
III-V materials etching

 Oxidation (or reduction) of semiconductor surface


- H2O2

Removal of soluble reaction product


- H3PO4, HNO3, H2SO4, HCl,

Dilute the etch solution with


- H2O

Extensively used recipe


- GaAs; H2SO4:H2O2:H2O and H3PO4:H2O2:H2O
- InP; HCl:H2O

Selective etching
- H2SO4:H2O2:H2O etches InGaAs and InGaAsP but not InP
- HCl:H2O etches InP but not InGaAs and InGaAsP
Anisotropic wet etch formulation
Alkali metal hydroxide etchants
- Examples : KOH, NaOH
- Typically 15 ~ 40 % concentration, diluent water or isopropanol
- 70 oC
- Selectivity
• (100) ; (111) about 400 : 1
- Etch rate: concentration, etch temperature, doping
• Generally, KOH tends to give very smooth (111) plane

TMAH Etching
-MOS/CMOS compatible
•No alkali metals
-Anisotropy: (111) : (110) ~ 1 : 10 to 1 : 35
-Typical recipe
•250mL TMAH (25 %)
•375ml H2O
•At 90oC
•Etch rate : 1 m/min
Anisotropic wet etch formulation
Anisotropic Si wet etching

Si etching depending on the orientation

 More bonds to break  slower etch rate


In some etchants
- (111) slowest – densest, more bonds
- (110), (100) fastest – most sparse,
fewer bonds

 This orientation dependence works with


KOH:H2O:IPA (24:13:63)

 Strong orientation dependence can be used


to fabricate submicron device structure

Mask materials: (1) SiO2 (2) Si3N4


Selectivity of Si over Si3N4 :  1000
Si over SiO2 :  100
Anisotropic Si wet etching
Si: diamond cubic crystal structure (FCC)

a = 5.43 Å

View in <100> direction


View in <110> direction
View in <111> direction
How to use the CUBE in anisotropic etching
Homework

- How many silicon atoms in (100), (110) and (111) crystal facet per cm 2?
Nano-Bridges: A Practical
Solution to Interconnecting
Nanoscale Devices

Shashank Shama
Saif Islam
Ted Kamins

At Hewlett-Packard Lab
Metal-catalyzed nanowire growth
Deposit metal
SiH4 H2
and anneal
Metal catalyst
particle (eg, Ti, Au)
Gas transport
Si H

SiSiSubstrate
Substrate

Si
Si nanowire
SiH 4

Metal
nanoparticle Catalyzed surface reaction:
-Diffusion (through or around nano-
Si nanowire
particle) and precipitation
Si Substrate Catalyst nano-particle can be in liquid or solid state
during nanowire growth
Expose to SiH4 gas
at 600-700C
Si nanowires on Au nanoparticles: [111] growth
direction
(100) substrate (111)-4 substrate
500 nm 500 nm

[111] [111]
[111]

Si(001) Si(111)

Good electrical and mechanical connection to the substrate


T I Kamins et. al.
Vertical 111 silicon sidewalls

110-SOI Wafer

Si [111]

3m 20m
•Smooth, perfectly vertical Sidewalls (111 crystal planes)
•No lateral etching in <111> direction
Nanowire on vertical (111) silicon planes

Si-Au Alloy

Alloy at 625o in H2
Direction of growth Growth at 635o
Pressure 10 Torr
SiH4 15 sccm
H2 3 slm
HCl 15sccm
2m
First demonstration of self-assembly of
nano-bridges

Saif Islam et. al., Nanotechnology 15 (2004) L5–L8

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