Measurement of Resistivity and determination of Energy Band Gap

using the Four Probe Method

Rahul Devarakonda (2018/UG/019)
Lab Partner: Akshay Pal (2018/UG/001)
16th March, 2021

Contents
1 Introduction 2

2 Theory 3
2.1 Concentration of Intrinsic Carriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2 Conductivity of an Intrinsic Semiconductor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3 Procedure 4

4 Observations and Results 5

5 Sources of Error 7

6 Appendix 8

1
1 Introduction
The Four Probe Method is one of the standard and most widely used method for the measurement of resistivity
of semiconductors. The experimental arrangement is illustrated. In its useful form, the four probes are collinear.
The error due to contact resistance, which is specially serious in the electrical measurement on semiconductors,
is avoided by the use of two extra contacts (probes) between the current contacts. In this arrangement the
contact resistance may all be high compare to the sample resistance, but as long as the resistance of the
sample and contact resistances are small compared with the effective resistance of the voltage measuring device
(potentiometer, electrometer or electronic voltmeter), the measured value will remain unaffected. Because of
pressure contacts, the arrangement is also specially useful for quick measurement on different samples or sampling
different parts of the same sample.

Figure 1: Schematic of the apparatus

The method described here inhibits the production of minority carriers (which will affect the potential of other
contacts and modulate the resistance of the material) and also offers several other advantages. It permits
measurements of resistivity in samples having a wide variety of shapes, including the resistivity of small volumes
within bigger pieces of semiconductor. In this manner the resistivity of both sides of p-n junction can be
determined with good accuracy before the material is cut into bars for making devices. This method of
measurement is also applicable to silicon and other semiconductor materials.
The basic model for all these measurements is indicated below. Four sharp probes are placed on a flat surface
of the material to be measured, current is passed through the two outer electrodes, and the floating potential is
measured across the inner pair. If the flat surface on which the probes rest is adequately large and the crystal is
big the semiconductor may be considered to be a semi-infinite volume. To prevent minority carrier injection and
make good contacts, the surface on which the probes rest, maybe mechanically lapped.

Figure 2: Model for the Four Probe Resistivity Measurement

The experimental circuit used for measurement is illustrated schematically in Fig.1 A nominal value of probe
spacing which has been found satisfactory is an equal distance of 2.0 mm between adjacent probes. This permit
measurement with reasonable current of n-type or p-type semiconductor from 0.001 to 50 Ω cm
To use the Four-Probe Method, the following Assumptions have been made:
1. The resistivity of the material is uniform in the area of measurement.

2
 2. If there is minority carrier injection into the semiconductor by the current - carrying electrodes most
of the carriers recombine near the electrodes so that their effect on the conductivity is negligible. (The
measurements were made on surface which have a high recombination rate, such as mechanical lapped
surfaces).

3. The surface on which the probes rest was flat with no surface leakage.
4. The four probes used for resistivity measurements contact the surface at points that lie in a straight line.
5. The diameter of the contact between the metallic probes and the semiconductor should be small compared
to the distance between probes.

6. The boundary between the current-carrying electrodes and the bulk material is hemispherical and small in
diameter.
7. The surfaces of the semiconductor crystal may be either conducting or nonconducting.
• A conducting boundary is one on which a material of much lower resistivity than semiconductor (such
as copper) has been plated.
• A non-conducting boundary is produced when the surface of the crystal is in contact with an insulator.

2 Theory

Figure 3: Circuit Used for resistivity measurements

In figure 3, the four probes S1, S2, S3, and S4 are equally spaced. Current I is passed through the outer
probes (1, 4) and the floating potential V is measured approx the inner pairs of probes (2, 3).

The potential difference between probes 2 and 3 can be written as

Iρ0
V = (1)
2πs
Where ρ0 is the resistivity of the material, I is the amount of current passing through the material. Therefore,
V
ρ0 = 2πs (2)
I
Since the thickness of the crystal is very small compared to the probe distance a correction factor for it has to
be applied.
ρ0 ρ0
ρ= = (3)
G7 f ( ws )

Here, f ( ws ) → Correction term, which is G7 = f ( 0.050

0.2 ) = 5.89

2.1 Concentration of Intrinsic Carriers

The concentration of intrinsic carriers in the conduction band of a semiconductor is
 ∗ 3  
me kB T 2 µ − Eg
n=2 exp (4)
2π~2 kB T

3
And the concentration of holes in the valence band of a semiconductor is
 ∗ 3  
mh kB T 2 µ
p=2 exp – (5)
2π~2 kB T

From (4) and (5), we get

 3  
kB T 3 Eg
np = 4 (m∗e m∗h ) 2 exp – (6)
2π~2 kB T

Equation (6) has no involvement with the Fermi level µ, and thus is known as the Law of Mass Action. Where
m∗e →Effective mass of an electron, m∗h →Effective mass of a hole, Eg →Band Gap.
For intrinsic crystals, the number of electrons is equal to the number of holes. This is because the thermal
excitation of electrons leave behind a hole in the valence band.
 3  
kB T 2 ∗ ∗ 34 Eg
ni = p i = 2 (me mh ) exp – (7)
2π~2 2kB T

2.2 Conductivity of an Intrinsic Semiconductor

The electrical conductivity will the sum of the contributions by the electrons and holes

σ = ni eµe + pi eµh (8)

Where e is the charge of an electron, ni is the number of electrons, pi is the number of holes, µe and µh are the
average velocities acquired by the electrons and the holes respectively (also called mobility).
For an intrinsic semiconductor,
  32  
kB T 3 Eg
σ = ni e(µe + µh ) = 2 (m∗e m∗h ) 4 e(µe + µh ) exp – (9)
2π~2 2kB T
 
3 Eg
= (Const.)T 2 (µe + µh ) exp – (10)
2kB T

kB

32 3
Here, Const. = 2 2π~ 2 (m∗e m∗h ) 4 e, which is a constant.
3
The factor T 2 and the mobilities change relatively slow with temperature compared with the exponential term,
and hence the logarithm of resistivity ρ = 1/σ varies linearly with T1 . The width of the energy gap may be
determined from the slope of the curve. Thus, we have,

Eg
ln ρ = − ln (Const.) (11)
2kB T

3 Procedure
1. We put the sample on the base plate of the four probe arrangement, unscrew the pipe holding the four
probes and let the four probes rest in the middle of the sample. We then applied a very gentle pressure on
the probes and tightened the pipe in this position, and then checked the continuity between the probes for
proper electrical contacts.
2. The outer pair of probes (red/black) which leads to the constant current power supply and the inner pair
(yellow/green) which lead to the probe voltage terminals were connected.
3. We then place the four probe arrangement in the oven and fix the thermometer in the oven through the
hole provided.
4. The ac mains of Four Probe Set-up is switched on and the digital panel meter was set to the current
measuring mode through the selector switch. In this position, the LED facing ’mA’ glowed. The current
was set to 5 mA.
5. The digital panel meter was set to measuring mode, and the PID control oven was switched on.
6. From the Voltage and Current, the resistivity was obtained and used to find the band gap.
7. A plot of ln ρ vs 1/T was plotted.

4
4 Observations and Results
A demonstration of finding the resistivity of a sample was done using a thin sheet of Aluminium1 .
The resistivity comes out to be (after correction) ρAl = 2.61 × 10–6 Ω cm.
We now using the four probe method tabulate the values for Germanium.
(Thickness of the Germanium crystal is 0.5 ± 2% mm)

Table 1: Tabulated values for Germanium

Temp (in °C) Temp. (in K) Voltage V ρ0 (inΩ cm) ρ (inΩ cm) ln(ρ) 1/T
73 346.16 0.196 48.5786 8.24764 2.109927 0.002889
74 347.16 0.186 46.1001 7.826842 2.057559 0.002881
76 349.16 0.18 44.613 7.574363 2.024769 0.002864
77 350.16 0.176 43.6216 7.406044 2.002296 0.002856
78 351.16 0.171 42.38235 7.195645 1.973476 0.002848
79 352.16 0.166 41.1431 6.985246 1.9438 0.00284
80 353.16 0.162 40.1517 6.816927 1.919409 0.002832
81 354.16 0.157 38.91245 6.606528 1.888058 0.002824
82 355.16 0.153 37.92105 6.438209 1.86225 0.002816
83 356.16 0.148 36.6818 6.22781 1.829025 0.002808
84 357.16 0.144 35.6904 6.059491 1.801626 0.0028
85 358.16 0.139 34.45115 5.849092 1.766286 0.002792
86 359.16 0.136 33.7076 5.722852 1.744467 0.002784
87 360.16 0.132 32.7162 5.554533 1.714614 0.002777
88 361.16 0.128 31.7248 5.386214 1.683843 0.002769
89 362.16 0.123 30.48555 5.175815 1.643997 0.002761
90 363.16 0.122 30.2377 5.133735 1.635833 0.002754
91 364.16 0.118 29.2463 4.965416 1.602497 0.002746
92 365.16 0.115 28.50275 4.839177 1.576745 0.002739
93 366.16 0.111 27.51135 4.670857 1.541343 0.002731
94 367.16 0.109 27.01565 4.586698 1.52316 0.002724
95 368.16 0.104 25.7764 4.376299 1.476203 0.002716
96 369.16 0.101 25.03285 4.250059 1.446933 0.002709
97 370.16 0.1 24.785 4.20798 1.436983 0.002702
98 371.16 0.098 24.2893 4.12382 1.41678 0.002694
99 372.16 0.095 23.54575 3.997581 1.385689 0.002687
100 373.16 0.093 23.05005 3.913421 1.364412 0.00268
101 374.16 0.09 22.3065 3.787182 1.331622 0.002673
102 375.16 0.089 22.05865 3.745102 1.320449 0.002666
103 376.16 0.086 21.3151 3.618862 1.28616 0.002658
104 377.16 0.083 20.57155 3.492623 1.250653 0.002651
105 378.16 0.081 20.07585 3.408463 1.226262 0.002644
106 379.16 0.079 19.58015 3.324304 1.20126 0.002637
107 380.16 0.077 19.08445 3.240144 1.175618 0.00263
108 381.16 0.075 18.58875 3.155985 1.149301 0.002624
109 382.16 0.072 17.8452 3.029745 1.108479 0.002617
110 383.16 0.07 17.3495 2.945586 1.080308 0.00261
111 384.16 0.069 17.10165 2.903506 1.065919 0.002603
112 385.16 0.067 16.60595 2.819346 1.036505 0.002596
113 386.16 0.065 16.11025 2.735187 1.0062 0.00259
114 387.16 0.063 15.61455 2.651027 0.974947 0.002583
115 388.16 0.061 15.11885 2.566868 0.942686 0.002576
116 389.16 0.06 14.871 2.524788 0.926157 0.00257
117 390.16 0.058 14.3753 2.440628 0.892255 0.002563
118 391.16 0.056 13.8796 2.356469 0.857164 0.002556
119 392.16 0.055 13.63175 2.314389 0.839146 0.00255
120 393.16 0.053 13.13605 2.230229 0.802104 0.002543
121 394.16 0.052 12.8882 2.188149 0.783056 0.002537
Continued on next page
1 The data has been moved to the Appendix

5
 Table 1: Tabulated values for Germanium

Temp (in °C) Temp. (in K) Voltage V ρ0 (inΩ cm) ρ (inΩ cm) ln(ρ) 1/T
122 395.16 0.05 12.3925 2.10399 0.743835 0.002531
123 396.16 0.049 12.14465 2.06191 0.723633 0.002524
124 397.16 0.048 11.8968 2.01983 0.703013 0.002518
125 398.16 0.047 11.64895 1.97775 0.68196 0.002512
126 399.16 0.045 11.15325 1.893591 0.638475 0.002505
127 400.16 0.044 10.9054 1.851511 0.616002 0.002499
128 401.16 0.043 10.65755 1.809431 0.593013 0.002493
129 402.16 0.042 10.4097 1.767351 0.569482 0.002487
130 403.16 0.041 10.16185 1.725272 0.545385 0.00248
131 404.16 0.04 9.914 1.683192 0.520692 0.002474
132 405.16 0.39 96.6615 1.89942 0.641549 0.002468
133 406.16 0.038 9.4183 1.599032 0.469399 0.002462
134 407.16 0.037 9.17045 1.556952 0.44273 0.002456
135 408.16 0.036 8.9226 1.514873 0.415331 0.00245
136 409.16 0.035 8.67475 1.472793 0.387161 0.002444
137 410.16 0.034 8.4269 1.430713 0.358173 0.002438
138 411.16 0.033 8.17905 1.388633 0.32832 0.002432
139 412.16 0.032 7.9312 1.346553 0.297548 0.002426
140 413.16 0.031 7.68335 1.304474 0.2658 0.00242
141 414.16 0.03 7.4355 1.262394 0.23301 0.002415
142 415.16 0.03 7.4355 1.262394 0.23301 0.002409
143 416.16 0.029 7.18765 1.220314 0.199108 0.002403
144 417.16 0.029 7.18765 1.220314 0.199108 0.002397
145 418.16 0.028 6.9398 1.178234 0.164017 0.002391
146 419.16 0.027 6.69195 1.136154 0.127649 0.002386
147 420.16 0.026 6.4441 1.094075 0.089909 0.00238
148 421.16 0.025 6.19625 1.051995 0.050688 0.002374
149 422.16 0.025 6.19625 1.051995 0.050688 0.002369
150 423.16 0.024 5.9484 1.009915 0.009866 0.002363
151 424.16 0.024 5.9484 1.009915 0.009866 0.002358
152 425.16 0.023 5.70055 0.967835 -0.03269 0.002352
153 426.16 0.023 5.70055 0.967835 -0.03269 0.002347
154 427.16 0.022 5.4527 0.925756 -0.07715 0.002341
155 428.16 0.022 5.4527 0.925756 -0.07715 0.002336
156 429.16 0.021 5.20485 0.883676 -0.12367 0.00233
157 430.16 0.021 5.20485 0.883676 -0.12367 0.002325
158 431.16 0.02 4.957 0.841596 -0.17246 0.002319
159 432.16 0.02 4.957 0.841596 -0.17246 0.002314
160 433.16 0.019 4.70915 0.799516 -0.22375 0.002309
161 434.16 0.019 4.70915 0.799516 -0.22375 0.002303
162 435.16 0.019 4.70915 0.799516 -0.22375 0.002298
163 436.16 0.018 4.4613 0.757436 -0.27782 0.002293
164 437.16 0.018 4.4613 0.757436 -0.27782 0.002287
165 438.16 0.018 4.4613 0.757436 -0.27782 0.002282

6
The ln ρ vs 1/T plot for Germanium is given below:

Figure 4: ln ρ vs 1/T

From, Eqn.((11)), the slope of the plot is

ln ρ Eg
1 = = 4052.21 ± 20.63 K (12)
T
2kB

Thus, EgGe = 0.698 ± (3.5 × 10−3 ) eV

5 Sources of Error
• The formula for ρ is valid for semi-infinite surfaces (samples with very large surface area) compared to the
probe distance.
• The semiconductor might have slight amounts of dopants in it.

• For Aluminium, the commercial grade Aluminium foil was used instead of pure Aluminium.
• Since the Aluminium foil is quite thin, there maybe an error introduced while measureing its thickness.

7
6 Appendix
For Aluminium, we take a sample with 16 foils with the thickness of the whole stack being 0.16 ± 0.01 mm.

Table 2: Finding the Resistivity of Aluminium

Current(I)(mA) Voltage(V )(mV) (V /I) ∗ 1000

52.1 0.015 0.287908
60.9 0.018 0.295567
65.3 0.02 0.306279
70.1 0.021 0.299572
75.5 0.023 0.304636
80.7 0.025 0.309789
85.6 0.027 0.315421
90 0.029 0.322222
95.2 0.031 0.32563
100.3 0.032 0.319043
104.6 0.034 0.325048
105.6 0.035 0.331439
109.6 0.036 0.328467
111.5 0.037 0.331839
120.9 0.039 0.322581
125.1 0.041 0.327738
130.5 0.043 0.329502
135.1 0.044 0.325685
140.3 0.046 0.327869
145.8 0.048 0.329218
155 0.051 0.329032
170.6 0.057 0.334115
185.5 0.063 0.339623
190.7 0.065 0.34085

We plot the Voltage vs Current plot for Aluminium.

Figure 5: Resistivity of Aluminium

We get the resistivity for Aluminium (ρ0 ) to be ρ0 = 4.03 × 10−4 Ω cm. In this case, the correction function(G7 )
is G7 = 154. Thus, the corrected resistivity for Aluminium(ρAl ) is ρAl = 2.61 × 10−6 Ω cm.