MSE 464: Band-Gap Engineering in Sputter-Deposited ScxGa1-xN

By Khari Amos

Introduction
Bandgap engineering plays a significant role in the world of optoelectronics, solar cell

efficiency, sensors, resistors, and semiconductors. A band-gap is the energy required to excite an

electron from the Valence Band to the Conduction Band in solid state physics and chemistry.

The ability of adjusting this characteristic in a material ranged from strain energy, composition,

thickness, and substrate. In this overview, the band-gap is observed in sputter-deposited ScxGa1-

xN on a quartz substrate. This paper observes the crystallography and band-gap energy using X-

Ray Diffraction (XRD) to find the chemical and physical interaction between the bilayer and

alloy film.

Application and Pre-Experimentation

Nitride semiconductors are mostly researched for their application in optoelectronics.

Gallium Nitride is useful in the electronic application due to the lack of mid gap states within its

band-structure. This means it takes a smaller amount of energy to excite the electron to the

conduction band and prevents a weakly conducting band gap (V. I. Kilmov, 486). Scandium

Nitride is observed in this experiment with the intention to replace Indium Nitride in InxGa1-xN

due the low melting point (relative to Sc). With this substitution of material, the film will be able

to withstand more intense and aggressive environments such as nuclear reactors. The chemical

interaction is important during the application of thin films because these characteristic effects

the macro-electronic and engineering behavior greatly. While InN and GaN shared the same

crystallographic structure (wurtzite/hexagonal), ScN has a rock-salt structure (similar to NaCl).

While the lattice spacing matches with GaN, overall crystal structure could result in
microcrystalline (alloy) or amorphous microstructure. Due to the spatial inconsistencies of bond

length and bond angle within an amorphous material, the edges of the conduction and valence

band tend to be broadened (raising the effective mass which is not wanted for electronic

interactions). This characteristic creates a “band tail” located in the Tauc plot (Morgaki K.,

2017). The Tauc plot is the graphical determination of the optical bandgap in semiconductors.

This plot is often used to characterize the optical properties of amorphous materials (J. Tauc,

1316). The individual band-gaps of InN and ScN are .7 eV and roughly 2.1 eV, so with the

substitution of Sc, the band-gap energy range will decrease from .7-3.4 eV to about 2-3.4 eV

assuming the compounded bandgap interaction is the same.

Experimentation and Results

The deposition method chosen in this experiment was Reactive Sputtering holding the

substrate temperature between the range of 300 and 675K on a quartz substrate growing the film

between the range of 350 to 500nm. The concentration of Sc was varied between 20-70% so we

can observe the characteristic band-gap energy relative to the concentration of Sc. We notice the

bandgap energy decreases with an increase of Sc in the film. We can also notice the bandgap

energy of pure ScN on the quartz substrate between 2-2.5eV.

 Figure 1&2. Scandium concentration v. Bandgap energy (Left). Energy v. the Absorption
Coefficient (Right). We observe the “band tail”, an amorphous structure characteristic, in this
graph.

Under XRD, the films showed very weak to no crystalline structure suggesting the structure was

microcrystalline or amorphous (M. E. Little, 2891). The “band tail” characteristic (between 1.4

and 3 eV on Figure 2) is common in this structure due to their electronic states changing from

localized to delocalized at a critical boundary. This is called the mobility edge and gap (Morgaki

K., 2017). The mobility gap is caused by a lack of long-range order and other defects in the

amorphous structure. The exposure to light creates metastable phases in bandgap that degrade

material. If an amorphous structure of the film is the case, this material would be counter

productive for applications like semiconductors and solar cells.

A second experiment to determine if phase segregation is present between GaN and ScN

was conducted by creating bilayers and observing their interaction under XRD. This is important

because phase segregation leads to non-homogeneity in crystal structure resulting in amorphous

layers. A thin film with one single layer of GaN and another of ScN with a total thickness of

300nm.
 Figure 3. Optical absorption of ScN and GaN layers in alloy thin films. Arrows indicate
signature feature seen in bilayer films.
The results of this test show that only in the bilayer samples exhibited the distinct ‘hump’ at 3.5-

4 eV. This hump is the characteristic of bilayer films (and the signature of phase-segregation)

due to small structures at low energy at the film interface. While the first Concentration XRD

(Figure 2) resulted in amorphous crystallographic structure, and the second Bilayer XRD

(Figure 3) lacked the characteristics of phase segregation, we find the physical properties of the

film is inconclusive. In the bilayer XRD, an electronic interaction implies the bandgap of the

tested film to lie between 2 and 3.5 eV that varies linearly with the increase in Sc composition

(M. E. Little, 2892).

Conclusion

While finding the bandgap (2-3.5 eV) of this alloy film was important, finding the crystal

structure of the film is a necessity prior to application. As previously stated in the paper,

amorphous films are not ideal for optoelectronic applications like semiconductors or solar cells.

Identifying methods to make this interaction more cohesive will increase the applicability for the

alloy.
Sources

1) M. E. Little, M. E. Kordesch, Band-gap Engineering in Sputter-Deposited ScxGa1-xN.

Published May 2001.

2) Morigaki K., Ogihara C. (2017) Amorphous Semiconductors: Structure, Optical, and

Electrical Properties. In: Kasap S., Capper P. (eds) Springer Handbook of Electronic

and Photonic Materials. Springer Handbooks. Springer, Cham

3) Tauc, J. (1968). Optical properties and electronic structure of amorphous Ge and Si.

Materials Research Bulletin. 3: 37–46.

4) V. I. Kilmov (2011). Role of mid-gap states in charge transport and photoconductivity in

semiconductor nanocrystal films. Physics.