A Report on

Self / Unintentional Doping of Metal Oxide based Semiconductors

BIRLA INSTITUTE OF TECHNOLOGY & SCIENCE, PILANI

DECEMBER 2021

Submitted to:
Dr Subhashis Gangopadhyay

Submitted by:

Aditi Singh 2018B5A40700P

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 ACKNOWLEDGEMENT

I would like to express my sincere gratitude to Dr Subhashis Gangopadhyay, Associate

Professor, Birla Institute of Technology and Science, Pilani, for his continuous guidance and
support in this project. His enthusiasm, motivation, and knowledge inspired me to do my best.
I would also like to thank my peers who helped me gain deep insights into the topic through
fruitful discussions.

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 ABSTRACT

Because of their charge transport capabilities, metal oxide semiconductors are a distinct class of
materials. They differ from traditional covalent semiconductors, which have a large difference in
charge carrier transport due to the interaction between the metal and oxide orbitals. This report
aims to study the material properties of these metal oxide based semiconductors that give them
the n-type-type and p-type conductivity. It also looks at gas sensors, their need and applications,
and the use of metal oxide based semiconductors in the fabrication of these gas sensors. The
properties of the semiconductors that make them suitable for gas sensing, as well as their gas
sensing mechanisms are also studied.

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 INTRODUCTION

When compared to traditional covalent semiconductors such as silicon, metal oxide

semiconductors represent a distinct class of materials due to their electronic charge transport
capabilities. Metal oxide semiconductors are valence compounds with a strong ionic bonding
strength. The metal (M) ns and oxygen (O) 2p orbitals dominate their conduction band minimum
(CBM) and valence band maximum (VBM), respectively.

One of the most popular types of sensors is gas sensors. Gas sensors are employed in a variety of
fields to detect chemicals at concentrations below the human olfactory limit (ppm, ppb, or even
ppt), or gases that represent a concern to human health even at lower concentrations. Metal oxide
semiconductors (MOSs) outperform conventional gas sensing materials thanks to their better
physical and chemical capabilities as well as their unique structure. Because these materials have
a large band gap, they can have a wide range of electrical properties.

Semiconductor metal oxides have been utilised as conductive gas sensors since the 1950s, when
they were first proposed. It was discovered in the 1950s that changes in the composition of the
neighbouring atmosphere can have a considerable impact on the near-surface electrical
characteristics of semiconductor materials. Resistive gas sensors have gotten a lot of attention
since then because of their low cost, simple completion, online monitoring, and high reliability
for real-time control systems and a variety of practical applications. In 1968, semiconductor-type
gas sensors were used for the first time in household gas leak detectors. The Figaro TGS was the
first such sensor (Taguchi gas sensor).

This review tries to look at the various material properties of metal oxides that give them n-type
or p-type conductivity, and also the properties that make them the most popular choice for gas
sensors.

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 CAUSES FOR UNINTENTIONAL CONDUCTIVITY

● p-type metal oxide based semiconductors

➢ Copper (I) Oxide (Cu₂O)

In Cu2O, the p-type conductivity can be attributed to:
➔ Cu Vacancies: Most studies suggested that Cu vacancy is a deep acceptor,
although the reported ionization energies are rather dispersive, in the range
of ∼0.2 to 0.7 eV. Recently, both deep-level transient spectroscopy
experiments and hybrid-density-functional calculation found that there are
two acceptor states with ionization energy of 0.45 and 0.25 eV,
corresponding to the simple and split Cu vacancy geometry, respectively.

➢ Nickel (II) Oxide (NiO)

Like Cu2O, the conductivity of undoped NiO is also a result of Ni
vacancies. However, Ni vacancy is a deep acceptor, and therefore the
achievable conductivity and the hole concentration is limited.

➢ Tin(II) oxide (SnO):

In SnO, the p-type conductivity results from Sn vacancies. The low
formation energy of Sn vacancies makes SnO a p-type metal oxide
semiconductor.

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● n-type metal oxide based semiconductors

➢ Zinc Oxide (ZnO):

In ZnO, the possible reasons for the unintentional semiconductivity are:
➔ Oxygen Vacancy: Oxygen vacancy acts as donor and is indeed easy to
form in ZnO lattice according to either experimental observations or
theoretical calculations.
➔ Hydrogen Impurity: H atoms act as shallow donors either as interstitials or
substituting oxygen sites.

➢ Tin Oxide (SnO2):

The origin of the n-type conductivity in undoped SnO2 has been under
debate for a long time. A couple of possible reasons are:
➔ Intrinsic Point Defects: such as oxygen vacancy and tin interstitial.
➔ Extrinsic Impurity: such as hydrogen.

➢ Indium(III) oxide (In₂O₃):

It is generally found that unintentionally doped In2O3 films and bulk
crystals show reasonable n-type conductivity with electron concentration of
1017 to 1019 cm−3. The possible reasons for this are:
➔ Oxygen Vacancies: VO is regarded as a shallow donor based on the
experimental results of annealing In₂O₃.
➔ Hydrogen Atoms: They occupy interstitial sites instead of
substituting oxygen.
➔ Surface Electron Accumulation Layer

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 GAS SENSORS

Introduction

Humans perceive the surrounding environment and other pertinent information in a variety of
ways. We've designed a wide range of sensors to push the boundaries of our own perceptions.
Sensors can assist us in identifying various types of relevant information in the surrounding
environment and converting that information into electrical signals or other essential kinds of
information output via appropriate processes to fulfil varied production and life needs. One of
the most prevalent types of sensors is gas sensors.

Gas sensors' principal purpose is to detect gases at concentrations lower than the human
olfactory limit (ppm, ppb, or even ppt), or gases that are hazardous to human health even at
lower concentrations, and they are widely utilised in a variety of fields.

Gas sensors are commonly believed to provide a measurement of the concentration of an analyte
of interest, such as CO, CO2, NOx, or SO2, without addressing the numerous underlying
techniques, such as optical absorption, electrical conductivity, electrochemical (EC), and
catalytic bead. Many other gas sensors, on the other hand, detect a physical feature of the
environment surrounding them, such as simple temperature, pressure, flow, thermal conductivity,
and specific heat, or more complex qualities for gaseous fuels, such as heating value,
supercompressibility, and octane number. The latter may necessitate capital-intensive (engines)
or destructive testing, such as combustion, or the measurement of a number of characteristics to
be used as inputs to a correlation with the complicated property of interest.

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Applications

❏ Industrial Safety: Dangerous gases must be recognized to safeguard the safety of those
working in hazardous situations. As a result, gas sensors are widely utilized in industries
to prevent accidents caused by gas leakage.

❏ Medical and Life-Science Industries: Many gas sensors are so precise, consistent, and
reliable that they may be easily integrated into fields like incubation, neurology,
respiration, and capnography, among others.

❏ Transportation Industries: Within the previous 5-10 years, the transportation industry
has been aggressively seeking new sensor technologies. Typically, these industries are
interested in measuring carbon dioxide (CO2) and oxygen (O2) concentrations in cargo,
such as for dry ice transportation, or analyzing shipping containers to determine the
effects on product life span.

❏ Aerospace Industries: Aerospace is a unique business in that it requires the use of gas
sensor technologies to assess both oxygen and carbon dioxide gas concentrations. Gas
sensors are used in aerospace environments to monitor in-flight conditions and air quality
maintenance to ensure crew productivity and overall passenger comfort.

❏ Breath Analysis: Exhaled breath testing is a common illness monitoring technique that
replaces blood and urine samples, which can be uncomfortable for patients. Gas
biomedical sensors for non-invasive and point-of-care diagnostic devices have made
rapid progress in monitoring exhaled breath indicators. Due to their unique qualities, such
as high sensitivity, simple fabrication, miniaturization, mobility, and real-time
monitoring, metal oxide-based biomedical gas sensors have gotten a lot of interest among
gas sensors.

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Role of Metal Oxides

Metal oxide semiconductors (MOSs) outperform conventional gas sensing materials due to their
better physical and chemical capabilities as well as their unique structure. Because these
materials have a large band gap, they can have a wide range of electrical properties. The material
size has a significant impact on the properties of MOSs. The nanoeffect, in particular, causes a
material's properties to be distinct at the nanoscale. For example, the electrical characteristics
alter dramatically, resulting in a good gas detecting material.

Furthermore, these materials have a large surface area per unit mass. When particles are smaller
than a nanometer, new physical and chemical features emerge. When the size of the material is
reduced, the specific surface area as well as the surface to volume ratio increase dramatically. In
addition, the size and geometry of semiconductor nanoparticles affect the movement of electrons
and holes. The demand for nanoparticles for gas sensor development is increasing due to their
high crystalline structure, noble metal doping ability, and competitive production rate.

Commonly used MOS gas sensing materials are\sdivided into n-type and p-type materials,
including ZnO, SnO2, MoO3, NiO and Cu2O. Furthermore, these MOSs have improved stability
and response times in high-temperature or severe conditions, which is important for practical
applications. Low-cost and simple manufacturing techniques are also major factors in the
material's success on the market.

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 GAS SENSING MECHANISM

Introduction

The sensing mechanism of gas sensor based on metal oxides semiconductors is mainly owing to
the variation of resistance when host materials are exposed to atmosphere containing target
gases. The creation of an electronic core–shell structure by oxygen adsorption is responsible for
the gas sensing properties of metal oxide semiconductors. The resistance of semiconductors is a
key factor in determining the physicochemical properties of metal oxides, and it varies based on
the physical nature of the metal oxide and the gaseous analyte.

Sensing Mechanism of n-type MOS based Sensors

❏ At high temperatures (>100 °C), oxygen molecules were adsorbed onto the surfaces of
n-type metal oxide semiconductors (e.g., SnO2 and ZnO).
❏ They thus ionised into oxygen species such as O2-, O-, and O2- by taking electrons from
the surfaces of the semiconductors.
❏ These species are known to be dominant at <150, 150–400 and at >400 °C, respectively,
which will induce to form an electronic core–shell structures where an n-type
semiconducting region exist in the cores and resistive electron depletion layer (EDL) at
the shells of the particles.

❏ The current carrier in n-type semiconductors is electrons (e−).

❏ Oxygen molecules adsorb onto the surface of the oxides and “grab” electrons from the
surface to form oxygen anions like O2−, and O− under ambient atmosphere and can
decrease the electron density and increase the resistance.
❏ When n-type semiconductor is exposed to reductive gases, such as CO, H2, CH4, C2H5OH
and acetone, electrons would flow back to depleted oxides through the surface reaction
between negative oxygen species and reductive gases
❏ For oxidizing gases such as Cl2,NOx, and SO2 , it can intensify the electron depletion and
cause an increase in resistance.

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The sensing mechanism of n-type MOS based gas sensors can be demonstrated with the example
of a ZnO based sensor. The figure here shows the development of resistance change of n-type
metal oxide immediately after the exposure of the sensor to H2, and also the calculated sensor
response based on the change of resistance. It can be seen that the response increased when the
concentration of H2 is increased.

Sensing Mechanism of p-type MOS based Sensors

❏ The adsorption of oxygen species in p-type metal oxide semiconductors forms the hole
accumulation layer (HAL) at the surface of the material.
❏ This again establishes the electronic core–shell configuration, forming the insulating
region at the cores and semiconducting HALs at the surface of these particles.

❏ For p-type metal oxides, the current carrier is holes (h+).

❏ The variation of resistance toward reductive gases and oxidizing gases is absolutely
opposite to n-type semiconductors.

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The sensing mechanism of p-type semiconductors is based on the change of hole transport
mechanism. Thus, the sensing behavior is opposite from the n-type MOS. The figure here shows
the dynamic response of laser-irradiated p-type NiO for the concentration of hydrogen in
1000-3000 ppm in the air at 175 degree C, and the the sensor response for 1000, 2000 and 3000
ppm of H2 and CH4 at 175 degree C.

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 REFERENCES

● Chemical Sensors and Biosensors: Fundamentals and Applications

● Metal oxide semiconductors and conductors (Haiping He, in Solution Processed
Metal Oxide Thin Films for Electronic Applications, 2020)
● Sources of Electrical Conductivity in SnO2
● Semiconducting Metal Oxides for Gas Sensing
● Gas sensing mechanisms of metal oxide semiconductors: a focus review
● Metal Oxide Gas Sensing Material and MEMS Process
● Metal-oxide-semiconductor based gas sensors: screening, preparation, and
integration

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