Electrodeposition

Q32:
(a)

- Most important issue:

a. Formation of voids due to the absence of organic additives.
b. Formation of voids due to low conformal structures creating cusping (prominent
for sputtering) / overhand (every layer add some to the overhang)
- Remedy:
a. Superfilling / bottom-up filling, to use organic additives (accelerator, leveler,
suppressor)
b.

(b)

(i)
a. Increase in temperature causes larger grains (not grain boundaries) (Thin film
growth)
b. Increased temperature causes increased convection & increasing diffusion
coefficient of all species bring more chemical species onto surface high
probability of organic additives becoming part of films
c. Increased temperature breakdown organic additives
(ii)
a. (out of syllabus) Decreased concentration undersupply of CU2+ to surface
Increased concentration polarization reaction on surface is faster than flux to
surface Smaller grains

(c)
a. Both linear and Tafael are under non-mass transport limited, but Linear region is
preferred since a variation in applied potential will not cause large variation in
cathodic current easier to control.
(d)
a. Corner has more electric field lines, vias do not have. Thus more electroplating
on the surface compared to that in the trenches. Thus current density will be
different over entire structure, concentrated on corners and edges & less in vias
& trenches.
* Adding additives can accelerate Cu filling in vias & trenches slow down
electroplating on the surface

Low dielectric constant materials

33. A certain polymer was added into a solution of methyl silsesquioxane (dielectric constant of
2.5). The mixture was first spin-coated onto the wafer, followed by heating successively on 3 hot
plates at 80C, 170C and 250C, and lastly cured at 400C in a furnace. However, the porous
methyl silsesquioxane (expected dielectric constant of 2.0) was not formed. Deduce what could
have gone wrong.
(Templating technique using polymer) Nanoscopic separation of porosion is absent:
1. There could be a reaction between methyl & polymer
2. 400C: to fully decompose porosion (question states that porosion is not fully decomposed)
due to decomposition temperature above 400C
3. Polymer used may not be organic, thus unable to be decomposed.
[9 marks, Apr 2007]
34. You are given silicon dioxide (dielectric constant of 3.9) and a methyl silsesquioxane (dielectric
constant of 2.5). There is a commercial need to develop a silicon oxide material having a dielectric
constant (k) of 1.8. In order to attain k of 1.8, porosity of 58% and 30% has to be incorporated into
silicon dioxide and methyl silsesquioxane respectively. Which of the two would you modify to reach
a dielectric constant of 1.8 and what would be the technical considerations in your choice?
30% - nanoporous (closed cells)
58% - mesoporous (opened cells)
problem with mechanical strength, poor thermal conduction, etc (Issues about porosity & their
solutions)
[16 marks, Apr2008]

35. A PECVD cold wall single wafer reactor has been used for the deposition of silicon dioxide (SiO2)
into high aspect ratio (>4:1) metal lines with spacing between metal lines less than 0.5m in
aluminium-copper based inter-metal deposition (IMD) applications from the following reaction:

Si(OC2H5)4 (TEOS) + O2

Deposition conditions: 325C, 2 torr, O2:TEOS ratio at 20:1, rf power 0.5W/cm2

(f) The silicon dioxide deposited has a dielectric constant of 3.9 (to 4.2). Using the same PECVD
reactor, how would you deposit a silicon dioxide-based film that has a dielectric constant between
2.7 and 3.4? How would you then confirm that the film is silicon dioxide-based?
FSG (for TEOS)
FTIR: look at the Si-O absorption/vibration
[8 marks, Apr 2009]

36. April 2014: Advanced aluminium interconnects that comprise metal lines having the top-down
film stack of TiN ARC/98%Al-2%Cu/TiN/Ti and spacing between metal lines as narrow as 0.1m are
to be fabricated. Two spin-on dielectrics, SOD (spin-on dielectric) A and SOD B, are evaluated for
use as an inter-metal dielectric (IMD) in these aluminium interconnects (should exceed 550, MP of
aluminium 650). The fabrication sequence for SOD A and SOD B is as follows: spin coating to a
thickness of 3000, hot plate baking at 80C, 150C and 230C at 1 minute duration at each
temperature, and finally curing in a furnace at 400C in a nitrogen ambient for 30 minutes.

+(a) The two figures below show the Fourier transformed infra-red (FTIR) spectra for SOD A and SOD
B respectively after curing.

10401080
Si-O-Si

3550 SiOH
bending

770
Si-C
850
Si-O

2900
C-H

940 Si-OH
stretching

SOD A

850
Si-O

SOD B

Interpret both FTIR spectra and deduce the type or identity of spin-on dielectric for SOD A
and SOD B.
-

SOD A: Silicates (pure Si-O)

SOD B: Alkyl silsesquioxane (Si-O plus alkyl groups, thus having Si-C bonds)
[6 marks]

(b) Comment on whether contact angle measurement could further help in the deduction of the
type or identity of the above two SODs materials.
-

Yes it helps, silicate is more hydrophilic thus larger contact angle

[3 marks]

(c) The refractive index measurements taken for SOD A before and after furnace curing at 400C
were shown to be unchanged. What would be your deduction of this experimental observation
and what would be your advice?
[7 marks]
-

Cross-linking between monomers, density increases, thus RI supposed to increase

940
Si-OH

*Refractive index: ratio of light passing through vacuum and over substance. More dense:
higher refractive index.
Deduction: 1. No cross-linking
Advice: 1. Trouble shooting check: Check furnace temperature is 400 deg & whether period
is 30min, whether furnace curing has been done at the correct conditions

(d) Two bare wafers were spin-coated and baked using 2000 SOD B from the same bottle. One
wafer was then placed in the curing furnace and the FTIR spectrum of the after-cured wafer
showed the spectrum for SOD B. The second wafer was placed in a different curing furnace and
the FTIR spectrum after curing showed the spectrum similar to SOD A. Deduce what has gone
wrong for the second wafer and propose a remedy. (The FTIR spectra are as shown in part (a)).
-

Si-C & C-H bonds are gone. Oxidization of Si-C bonds to Si-O. Alkyl-silsesquioxane oxidized to
silicates.
[4 marks]

(e) In the fabrication of single copper damascene interconnects, 15,000 thick of SOD A would be
used as a inter-metal dielectric (IMD) and would be deposited using a single spin coating. A
trench will be etched into SOD A, followed by wet cleaning with solvents and deionised water
and lastly by deposition of barrier metal and copper. What are the 3 issues relating to SOD A
during the fabrication, and what are the corresponding remedies?
-

Issue: Very thick coating induce cracking. Remedy: Use multiple coatings, but low
throughput and manufacturing cost increased.
Issue: Surface adhesion may be affected if previous layers of coats are not contaminant-free.
Bad spin pattern / uneven thickness may arise. Remedy: Clean the surface thoroughly during
each stage.
*Purpose of 400 deg is to: 1. Cross-linking 2. Remove hydrogen-bonded water. Issue: Thick
coat means that theres a high probability that water is not removed. Outgassing of
hydrogen-bonded water during subsequent high temperature barrier metal deposition that
may corrode the barrier metal. Poison via Remedy:
*Cu damascene reduces RC delay. SOD A: k value of silicate (~4.0) Issue: Dielectric
constant of SOD A is too high
[12 marks]

(f) The scanning electron micrograph (SEM) shows the deposition of spin-coated SOD B (topmost
layer) into the trenches (spacing) defined by the PECVD silicon dioxide layer.
SOD B
PECVD SiO2
PECVD SiO2

Metal

Metal

Line

Line

Void

Deduce two issues with respect to SOD B and suggest a shared remedy.
-

2 issues: 1. Non-planar 2. Void formation

Remedy: 1. Thermal reflow at 100deg-120deg change composition of alkyl
selsesquixane (SOD B) such that it has a polymer that can flow between 100deg-120deg
to achieve planarization.

[6 marks]
-

(g) Given that the dielectric constant of SOD B and air is 2.70 and 1.00 respectively, how
much porosity should be introduced into SOD B to decrease the effective dielectric constant
to 1.50?
Use equations (lecture notes)
[6 marks]

(h) List 3 advantages of the spin coating technology over the plasma enhanced CVD technology for
deposition of low dielectric constant materials.
-

Adv 1. PECVD: Non-stoichiometry (Spin-coating has stoichiometry)

Adv 2. Lower dielectric constant materials for spin-on than that for PECVD
Adv 3. Porosity can be introduced for spin-on technology
[6 marks]

37. Apr 2012: Silicon dioxide has been the choice dielectric for inter-metal dielectric (IMD).
(a) Suggest methodologies for the modifications to the film structure of silicon dioxide so as to
decrease its dielectric constant to between 1.5 and 3.0.
-

Decrease the density by introducing alkyl/aryl groups.

Introducing porosity into silicon dioxide by Templating technique using polymer (resulting in
closed-cell) / using Templating technique using surfactant as a porogen (resulting in open
cell) / Sol-gel technique
- *dont bring in organic low k material
[16 marks]
(b) A porous silicon dioxide material having a dielectric constant of 1.2 was dried using carbon
dioxide at 216K and 0.52 MPa. Would you anticipate any issue?
- 216K and 5.2 MPa triple point temperature, where drying of aerogel is not possible. Need
to be at 304K and 7.3MPa

High k Dielectrics
38. April 2012: A perpendicular flow single wafer ALCVD cold wall reactor was used to deposit a high
dielectric constant material, hafnium oxide, through the following reaction of
tetrakis[ethylmethylamino]hafnium (TEMAHf) with water vapour:

[Hf(NC2H5CH3)4] (TEMAHf) + H2O

Deposition conditions: 200C and 1.5 torr.

Nitrogen was used as the purging gas and mono-crystalline silicon was employed as the substrate.

(c) The hafnium oxide replaces silicon dioxide that has a dielectric constant of 4.0, has a gate
thickness of 30 and covers a gate area of 4x10-12 m2. What is the range of equivalent thickness at
the same gate area for the hafnium oxide assuming its dielectric constant can vary from 15 to 26?
(1 = 1 x 10-10m and the permittivity of free space can be assumed to be 1.0 F/m)
[6 marks]

(g) Compare the following hafnium precursors in terms of their effect on hafnium oxide film
composition: (1) TEMAHf (2) Hafnium tetrachloride (HfCl4) and (3) Hafnium tertiary-butoxide
([Hf(OC(CH3)3)4]), belonging to hafnium alkoxide family.
[6 marks]

(h) Deposition is normally performed by alternate introduction of TEMAHf and H2O into the ALCVD
reactor, with nitrogen purging of the reactor after introduction of each precursor. The first
precursor to be introduced in the normal deposition sequence is H2O. Two process events were
encountered:
(i) No nitrogen purging of the reactor after introduction of each precursor;
(ii) The first precursor to be introduced is TEMAHf instead of H2O.
Compared with the normal deposition, what would be your expected observations in the HfO2
film quality produced by these two process events?
[5 marks]

(i) Typically, a thin layer of hafnium silicate (HfSixOy) is deposited on silicon before hafnium oxide is
formed. Why is there a necessity to deposit hafnium silicate?
[2 marks]

(j) From X-ray photoelectron spectroscopy (XPS) studies, hafnium silicate was found to comprise a
Hf-O-Si-O bonding structure. You have the availability of nitrogen and the following ALCVD
precursors: [Hf(NC2H5CH3)4] (TEMAHf), H2O, SiCl4, Si(OC2H5) (TEOS) and (C4H9O)3SiOH. Explain your

reasoning for the choice of precursors. Engineer a deposition sequence to deposit hafnium
silicate that is high in throughput.
[4 marks]