UNVIERSITY OF TEXAS AT ARLINGTON

Spin coating, diffusion, and

four-point probe resistivity
Lab teacher: Dr. Donald Butler
Sumeet Jain (UTA Id: 1001159999)

Experiment #2
Abstract:
The aim of the experiment was to investigate the Diffusion concepts, RCA and HF cleaning
process, doping the wafer with solution containing phosphorous by spin coating, and to use the
four point probe measurement technique to calculate sheet resistance.

Objective:
We have to measure the weight of the wafer before and after doping. With this we diffuse the
phosphorous atoms into bare silicon wafer by timed heating the wafers at 1100 0C. We also
need to calculate the sheet resistance of the wafers, one before spin coating and then after at
each interval of heating, using four point probe technique.

Introduction:
Diffusion is the process in which impurities, called dopants, are added into the semiconductor
wafer. These impurities alter or modify the electronic properties of semiconductor materials.
Diffusion is carried out in two processes:
1. Pre-deposition:- Dopants are first deposited on to the surfaces by several methods like
Chemical Vapor Deposition (CVD), Low pressure CVD (LPCVD), Plasma enhanced CVD (PECVD),
Spin on dopant
2. Drive-in:- After pre-deposition, the wafers are placed into the furnace and heated which
cause the dopants to diffuse through the surface and into the substrate

Image1. Source-Plummer, Diffusion 2000

Doping techniques
CVD
Under CVD three different process is used- Atmospheric pressure CVD (APCVD), LPCVD, PECVD
In APCVD, gas deposition is used to create dopant oxide layer at certain temperature
In LPCVD, wafers are loaded in a boat having dummy wafers to maximize the growth conditions
of wafers. The gas flow is kept at a pressure around 350 mTorr
In PECVD, gas flow is controlled at 300oc and pressure of 1050 mTorr

Disadvantages of CVD: - 1. Two different furnaces were used, one for pre-dep and other for
drive-in
2. Having a stringent safety precaution for handling poisonous gases, thus both these thing
made the process very expensive

Ficks Law
Diffusion is a process by which the solute at a higher concentration moves from a lower
concentration.
High concentration

Low concentration

J
X

J=Flux (Rate of transfer of solute/area)

The above diagram shows that the rate of transfer of solute from a higher to lower
concentration region with J( =Flux)
Ficks First Law

D=diffusion constant
dc/dx =diffusion gradient
But there is no correct way to measure the current density of the impurity, thus the second law
helps with that
Ficks second law

dc(z,t)/dt =rate of change of dopant atom concentration

These two law govern the diffusion process

Spin on Dopant
It uses a dopant containing silicate dissolve in alcohol. It is sprayed on the substrate by spinning
Advantages of SOD: - 1. Only one type of furnace is used in this method
2. Spraying the dopant on substrate is done at room temperature
3. No need of toxic gases

image2. Spin coating

Image3. Diffusion furnace

Four point probe measurement

Four point probe method is used to calculate average resistance of a thin layer or a sheet by
passing current through the outside two probes and measuring the voltage from inside two
probes. Use of four probes instead of two eliminates the unwanted resistance (parasitic
resistance) of the probe through which current flows.

Image4.four point probe (courtesy wenner 1916)

The resistivity is given by =2sF V/I

V, I are voltage and current resp.
s= distance between two points
F=correction factor, F=F1F2F3
F1 corrects sample thickness
F2 corrects lateral dimensions
F3 corrects for probe placements relative to sample edges

Equipment:
1. Tweezers: These tweezers are especially designed for handling delicate and fragile Si wafers.
They are made from anti-magnetic, anti-acid steel with smooth surface
2. Teflon holder: Teflon holder helps to immerse Si wafers into HF acid solution as it does not
react with the solution
3. Spin coating machine: This is used for doping the bare Si wafer with impurity in Predeposition step

Image5. Spin coating mechanism

4. Scientific weigh machine: This is used to weigh the extremely light Si wafers before and after
doping

Image6. Scientific weighing machine

(image courtesy www.alibaba.com)

5. Four point probe tool: This machine is used to calculate the sheet resistance of Si wafer and
the carrier type of wafer
6. Diffusion Furnace: This furnace is used in drive in step to diffuse the dopant into the
substrate by baking the substrate at timed temperatures

Image7. Diffusion furnace

Experimental procedure: Chemicals used:

Hydrofluoric acid (HF), P505 SOD, sulfuric acid (H2SO4), hydrogen peroxide (H2O2), DI (deionized)
water (H2O), acetone (CH3)2CO, O2 and N2 gas, and Si wafer.

Wafers characteristics:
(100) Si-P type, single side polished
2 Diameter
Resistivity 1-10 -cm
Thickness 254-306 m

Safety precautions:
The chemicals used are highly dangerous and all the protocols and procedure must be
followed which were taught in safety seminar
HF is reactive with glass hence do not add HF in glass containers. Use Plastic containers
and wear rubber gloves, face shield, sleeves while handling HF
Skin contact should be avoided with P2O5 as it is toxic by ingestion

A. Calculating bare wafer sheet resistance Rs0

Measure the sheet resistance of the substrate at the center of the wafer using four point
probe tool

Image8. Four point probe tool

Place the wafer inside the four plot, with polished surface facing down, and place the pressure
disc over the wafer. Now close the flap and press the test resistance button and see the
resistance value on the display.
B. Pre-clean process
Step1: Mix H2SO4, and H2O2 with a volume ratio: 3 (H2SO4): 1 (H2O2)
(We took 600ml of acid and 200ml hydrogen peroxide).
We should always add acid to water. This is called piranha solution in which we immerse the Si
wafers for 10 minutes using a clean quartz wafer holder. After this take out the Si wafers and
rinse it rigorously with de-ionized water. Then we proceed to step 2 without drying the wafer

Image9. Acid hood

Step2: Mix hydrofluoric acid (HF) and DI water, in the ratio: 2% 1(HF): 98% (H2O)
Be very alert while using HF acid as it is highly dangerous when it comes in contact with the
body. Now dip the wafers in the solution using a Teflon boat (quartz boat erode when comes
in contact with HF) water flowing evenly over the surface and not forming beads or droplets
indicates clean wafer. This is because bare Si is hydrophobic, whereas SiO2/Si is hydrophilic
Step3: Measure the weight of the clean wafer and the carrier type and sheet resistance of the
wafer.
C. Spin coating
Cover the spinner with Aluminum foil and clean the spinner chuck with acetone and push the
chuck onto spindle. Then, place the wafer on the chuck with the wafer center perfectly aligned
with the center of the chuck. Check the wafer centering. Deposit approximately 0.5 ml P 2O5
using a dropper. With wafer nicely aligned with the center of the chuck, raise the speed to
3000 rpm for about 30 seconds for a uniform thick film. Now bake the wafer at about 110oC in
order to evaporate the remaining solvent

Image10. Spin coating tool

D. Diffusion and Diffusion data

Place the wafers in the Quartz V boat with 3mm spacing between wafers with coating sides
facing each other. Prepare the diffusion furnace by eliminating and water vapor and passing
dry N2 gas prior to diffusion. Now prepare a gas mixture of approximately 75% N2, 25% O2.
Insert quartz boat with wafers into the tube furnace for 15 minutes. The temperature of the
furnace is adjusted to 1100oC. After pre-deposition make a 10% HF solution and the wafer is
deglazed for 3 minutes. This step is used to remove any phosphorous silicate on the wafer.
Measure the sheet resistance and the carrier type of the wafer. After weighing again we
should get a weight difference with earlier reading which indicates amount of phosphorous
added to the wafer.
Now place the wafers into the furnace and heat the wafer at 1100 o C for 15minutes and
calculate the sheet resistance and the carrier type of the wafer. Repeat this step several times
and collect the data of sheet resistances at different time intervals. Plot the graph of (Rs/Rs0)2
Vs. ln(sqrtt) where t=time. Determine the value of diffusion coefficient D and compare the
value of D with the table given in textbook

Image11. Placing wafer into the diffusion furnace

Readings:
Sheet resistance of bare wafer
Sr #
F1
F2
F3

F4

F5

F6

F7

Fs

129

130.6

132.7

134.3

129.9

124.5

128.4

138.4

128.9

126.1

132.6

134.3

129.4

124.0

126.4

139.2

129.1

130.4

133.4

133.8

127.5

124.1

134.0

137.7

mean

129

129.03

132.9

134.13

128.93

124.2

129.6

138.43

Sheet resistance of wafer Pre-dep (after 15 min) p/n type

Sr #
F1
F2
F3
F4
F5

F6

F7

Fs

216 p

20.5 n

40.2 n

14.7 n

15.78 n

15.91 n

20.2 n

15.09 n

216 p

20.5 n

40.2 n

14.76 n

15.47 n

15.92 n

20.2 n

15.09 n

215 p

20.5 n

40.2 n

14.79 n

15.43 n

15.92 n

20.2 n

15.09 n

mean

216

20.5 n

40.2 n

14.75 n

15.56 n

15.92 n

20.2 n

15.09 n

Sheet resistance of wafer drive in (after 15 min) p/n type

Sr #
F1
F2
F3
F4
F5

F6

F7

Fs

162.1p

20.6 n

34.4 n

13.91 n

14.54 n

15.00 n

20.3 n

14.45 n

162.9p

20.6 n

34.4 n

13.93 n

14.55 n

15.02 n

20.3 n

14.44 n

162.6p

20.3 n

34.3 n

13.93 n

14.55 n

15.00 n

20.3 n

14.45 n

mean

162.53p

20.5 n

34.37 n

13.92 n

14.55 n

15.00 n

20.3 n

14.45 n

Group mean:-44.75

Group mean:-36.95

Sheet resistance of wafer drive in (after 30 min) p/n type

Sr #
F1
F2
F3
F4
F5

F6

F7

Fs

147.6 n

19.73 n

34.9 n

13.67 n

14.25 n

14.50 n

20.3 n

14.14 n

144.6 n

19.70 n

34.9 n

13.67 n

14.24 n

14.50 n

20.3 n

14.13 n

144.9 n

19.72 n

35 n

13.65 n

14.25 n

14.52 n

20.3 n

14.15 n

mean

145.7 n

19.72 n

34.93 n

13.66 n

14.25 n

14.51 n

20.3 n

14.14 n

Group mean:-34.65
Sheet resistance of wafer drive in (after 45 min) p/n type
Sr #
F1
F2
F3
F4
F5

F6

F7

Fs

138.1 n

19.9 n

32.5 n

13.51 n

13.89 n

14.31 n

20.9 n

13.88 n

139.1 n

19.88 n

32.5 n

13.52 n

13.89 n

14.31 n

20.9 n

13.88 n

130.9 n

19.91 n

32.5 n

13.52 n

13.9 n

14.31 n

20.9 n

13.86 n

mean

136.03 n 19.9 n

32.5 n

13.52 n

13.89 n

14.31 n

20.9 n

13.88 n

Sheet resistance of wafer drive in (after 60 min) p/n type

Sr #
F1
F2
F3
F4
F5

F6

F7

Fs

130.1 n

19.78 n

29 n

13.27 n

13.77 n

14.3 n

20.2 n

13.77 n

129.6 n

19.78 n

29 n

13.3 n

13.75 n

14.29 n

20.2 n

13.78 n

129.3 n

19.78 n

29 n

13.27 n

13.75 n

14.29 n

20.2 n

13.77 n

mean

129.67 n

19.78 n

29 n

13.27 n

13.75 n

14.29 n

20.2 n

13.77 n

Sheet resistance of wafer drive in (after 75 min) p/n type

Sr #
F1
F2
F3
F4
F5

F6

F7

Fs

122.8n

19.51 n

27.6 n

13.17 n

13.6 n

14.25 n

19.38 n

13.58 n

122.9 n

19.53 n

27.6 n

13.17 n

13.61 n

14.25 n

19.37 n

13.6 n

122.9 n

19.5 n

27.6 n

13.17 n

13.62 n

14.25 n

19.37 n

13.61 n

mean

122.9 n

19.51 n

27.6 n

13.17 n

13.61 n

14.25 n

19.37 n

13.6 n

Group mean:-33.11

Group mean:-31.71

Group mean:-30.50

Calculations:
(xj=junction depth, =resistivity, D=diffusion constant, Rs=sheet
resistance)

Semi-log graph for Wafer Fs

Semi-log graph for group mean

Comparison:

The theoretical value of D0 is 155.88 x 10-15 , while the value obtain by

graph =2.8x10-2, Thus there is a vast difference between the two
values
There is also a significant difference between group mean and wafer F s
Q0 value obtained is 1.6x1016cm-2
wt. of bare wafer- wt. of wafer after glazing =0.0000168 grams

Sources of Error:

While spin coating dopant was not evenly distributed over the wafer
which was one of the source of error
More number of readings could have provided more accurate data
Also the atmospheric impurities, which cannot be completely
eliminated, added to error
The spin coating tool was outdated and modern updated machinery
could have helped reducing error

Conclusion:
Thus, we learn the diffusion process in detail and understood the various
factors involved from cleaning to doping to calculation of sheet resistance.
We also saw a significant difference in the theoretical and practical value of
the Diffusion coefficient
References:
Silicon Research and Technology Laboratory, School of Physics,
University Sains Malaysia,11800 Penang, Malaysia
http://www.advenergymat.de/
http://onlinelibrary.wiley.com/
Fabrication engineering at micro and Nano scale- Campbell