The manuscript describes a protocol for radio frequency magnetron sputtering of Bi2Te3 and Sb2Te3 thermoelectric thin films on glass substrates, which represents a reliable deposition method that provides a wide range of applications with the potential for further development.
Through various studies on thermoelectric (TE) materials, thin film configuration gives superior advantages over conventional bulk TEs, including adaptability to curved and flexible substrates. Several different thin film deposition methods have been explored, yet magnetron sputtering is still favorable due to its high deposition efficiency and scalability. Therefore, this study aims to fabricate a bismuth telluride (Bi2Te3) and antimony telluride (Sb2Te3) thin film via the radio frequency (RF) magnetron sputtering method. The thin films were deposited on soda lime glass substrates at ambient temperature. The substrates were first washed using water and soap, ultrasonically cleaned with methanol, acetone, ethanol, and deionized water for 10 min, dried with nitrogen gas and hot plate, and finally treated under UV ozone for 10 min to remove residues before the coating process. A sputter target of Bi2Te3 and Sb2Te3 with Argon gas was used, and pre-sputtering was done to clean the target's surface. Then, a few clean substrates were loaded into the sputtering chamber, and the chamber was vacuumed until the pressure reached 2 x 10-5 Torr. The thin films were deposited for 60 min with Argon flow of 4 sccm and RF power at 75 W and 30 W for Bi2Te3 and Sb2Te3, respectively. This method resulted in highly uniform n-type Bi2Te3 and p-type Sb2Te3 thin films.
Thermoelectric (TE) materials have been attracting a considerable amount of research interest regarding their ability to convert thermal energy into electricity via the Seebeck effect1 and refrigeration via Peltier cooling2. The conversion efficiency of TE material is determined by the temperature difference between the hot end of the TE leg and the cold end. Generally, the higher the temperature difference, the higher the TE figure of merit and the higher its efficiency3. TE works with no requirement for additional mechanical parts involving gas or liquid in its process, producing no waste or pollution, making it environmentally safe and considered a green energy harvesting system.
Bismuth telluride, Bi2Te3, and its alloys remain the most important class of TE material. Even in thermoelectric power generation, such as the recovery of waste heat, Bi2Te3 alloys are most commonly used due to their superior efficiency up to 200 °C4 and remain an excellent TE material at ambient temperature despite the zT value of more than 2 in various TE materials5. Several published papers have studied the TE properties of this material, which shows that the stoichiometric Bi2Te3 has a negative Seebeck coefficient6,7,8, indicating n-type properties. However, this compound can be adjusted to p- and n-type by alloying with antimony telluride (Sb2Te3) and bismuth selenide (Bi2Se3), respectively, which can increase their bandgap and reduce bipolar effects9.
Antimony telluride, Sb2Te3 is another well-established TE material with high figure of merit at low temperature. While stoichiometric Bi2Te3 is a great TE with n-type properties, Sb2Te3 has p-type properties. In some cases, the properties of TE materials often depend on the atomic composition of the material such as the n-type Te-rich Bi2Te3, but a p-type Bi-rich Bi2Te3 due to BiTe antisite acceptor defects4. However, Sb2Te3 is always p-type due to comparatively low formation energy of SbTe antisite defects, even in Te-rich Sb2Te34. Thus, these two materials become suitable candidates to fabricate p-n module of thermoelectric generator for various applications.
The current conventional TEGs are made of diced ingots of n-type and p-type semiconductors connected vertically in series10. They have only been used in niche fields due to their low efficiency and bulky, rigid nature. Over time, researchers have started to explore thin film structures for better performance and application. It is reported that thin film TE have advantages over their bulky counterpart such as higher zT due to their low thermal conductivity11,12, less amount of material and easier integration with integrated circuit12. As a result, niche TE research on thin film thermoelectric devices has been on the rise benefitting from the advantages of nanomaterial structure13,14.
Microfabrication of thin film is important to attain high performance TE materials. Various deposition approaches have been researched and developed including chemical vapor deposition15, atomic layer deposition16,17, pulsed laser deposition18,19,20, screen printing8,21, and molecular beam epitaxy22 to serve this purpose. However, the majority of these techniques suffer from high operation cost, complex growth process or complicated material preparation. On the contrary, magnetron sputtering is a cost-effective approach for producing high-quality thin films that are denser, exhibit smaller grain size, have better adhesion, and high uniformity23,24,25.
Magnetron sputtering is one of the plasma-based physical vapor deposition (PVD) processes which is widely used in various industrial applications. Sputtering process works when sufficient voltage is applied to a target (cathode), ions from the glow discharge plasma bombards the target and release not only secondary electrons, but also atoms of the cathode materials which eventually impact the surface of the substrate and condense as a thin film. Sputtering process was first commercialized in 1930s and improved in 1960s, gaining significant interest due to its ability to deposit wide range of materials using direct current (DC) and RF sputtering26,27. The magnetron sputtering overcomes low deposition rate and high substrate heating impact by utilizing magnetic field. The strong magnet confines the electrons in the plasma at or near the surface of the target and prevent damage to the formed thin film. This configuration preserves the stoichiometry and thickness uniformity of the deposited thin film28.
The preparation of Bi2Te3 and Sb2Te3 thermoelectric thin films using magnetron sputtering method has also been extensively studied, incorporating technique such as doping4,29,30 and annealing31 in the procedures, leading to different performance and quality. Study by Zheng et al.32 uses thermally induced diffusion method to diffuse Ag-doped Bi and Te layer which were sputtered separately. This method enables precise control on the composition of the thin films and the diffusion of Te by thermal induction protects the Te from being volatilized. The properties of the thin films can also be enhanced by pre-coating process33 before sputtering which results in better electrical conductivity due to high carrier mobility, consequently enhancing the power factor. Other than that, study by Chen et al.34 improved the thermoelectric performance of sputtered Bi2Te3 by doping Se via post-selenization diffusion reaction method. During the process, Se vaporizes and diffuses into the Bi-Te thin films to form Bi-Te-Se films, which results in 8-fold higher power factor than undoped Bi2Te3.
This paper describes our experimental setup and procedure for the RF magnetron sputtering technique to deposit Bi2Te3 and Sb2Te3 thin films on glass substrates. Sputtering was performed in a top-down configuration as shown in the schematic diagram in Figure 1, cathode was mounted at an angle to the substrate normal, leading to a more concentrated and convergent plasma to the substrate. The films were systematically characterized using FESEM, EDX, Hall effect and Seebeck coefficient measurement to study their surface morphology, thickness, composition, and thermoelectric properties.
Figure 1: A schematic of the top-down configuration sputter. The diagram was designed according, but not to scale, to the actual sputtering configuration available for this study including the arrangement of glass substrates to be sputtered viewed from the top. Please click here to view a larger version of this figure.
1. Substrate preparation
2. Sputtering method
Figure 2: Experimental setup. Photograph of the sputtering machine used in this study. Please click here to view a larger version of this figure.
3. Characterization
Cross-sectional micrographs of as-deposited Bi2Te3 and Sb2Te3 thin films were recorded using FESEM as shown in Figure 3A and Figure 3B, respectively. The surface of the overall film appears uniform and smooth. It is apparent that the crystal grains of the Bi2Te3 thin film were hexagonal, conforming the crystal structure of Bi2Te3 while the crystal grains of the Sb2Te3 thin film were composed of fine circular grains, similar to reported by Amirghasemi et al36. The cross-sectional images of both samples reveal densely packed particles growing on top of the substrate. The films had uniform thickness of approximately 1.429 ± 0.01 µm and 0.424 ± 0.01 µm for Bi2Te3 and Sb2Te3 thin films, respectively. The composition of the films was calculated from the EDX spectra in Supplementary File 1 and Supplementary File 2, and the values are tabulated in Table 1. The estimated values show that both thin films have stoichiometric ratios.
Carrier concentration and conductivity of the as-deposited thin films were determined at ambient temperature, while the absolute Seebeck coefficient was measured at temperature of approximately 50 °C. These results are presented in Table 2. The Bi2Te3 thin film shows negative absolute Seebeck coefficient and carrier concentration values confirming that the film was n-type and the Sb2Te3 film shows positive values for both absolute Seebeck coefficient and carrier concentration confirming its p-type conductivity.
Figure 3: FESEM cross-sectional images. (A) Cross-section image of Bi2Te3 with the film thickness.(B) Cross-section image of Sb2Te3 with the film thickness. Please click here to view a larger version of this figure.
Target | RF power, (W) | Absolute Seebeck coefficient, S (µV/K) | Carrier concentration, Nb (cm-3) | Conductivity, σ (Ω/cm) |
Bi2Te3 | 75 | -72.84 | -5.71 x 1020 | 108.96 |
Sb2Te3 | 30 | 238.83 | 1.44 x 1021 | 6.05 |
Table 1: EDX composition analysis. The table consists of the weight percent acquired from the EDX spectra, calculated atomic percent of each element, composition ratio, thickness, and deposition rate of both Bi2Te3 and Sb2Te3 samples.
Sample | Weight Percent (%) | Atomic Percent (± 0.5%) | Atomic Ratio | Thickness (± 0.01 µm) | Deposition Rate (nm/min) | ||
Bi2Te3 | (Bi) 51.0 | (Te) 42.8 | (Bi) 41.9 | (Te) 58.1 | [Bi]:[Te] 2:3 | 1.429 | 23.8 |
Sb2Te3 | (Sb) 39.6 | (Te) 59.7 | (Sb) 40.0 | (Te) 60.0 | [Sb]:[Te] 2:3 | 0.424 | 7.0 |
Table 2: Thermoelectric properties of microfabricated thin films. The table consists of the target materials, RF powers used, absolute Seebeck coefficients, Hall coefficients, and conductivity values of both Bi2Te3 and Sb2Te3 samples.
Supplementary File 1: Planar FESEM and EDX spectrum of Bi2Te3 with weight percent of each element. Please click here to download this File.
Supplementary File 2: Planar FESEM and EDX spectrum of Sb2Te3 with weight percent of each element. Please click here to download this File.
The technique presented in this paper presents no significant difficulty in setting up the equipment and implementation. However, several critical steps need to be highlighted. As mentioned in step 2.2.10 of the protocol, optimum vacuum condition is key to produce high quality thin films with less contamination as vacuum removes residual oxygen in the chamber37. The presence of oxygen can cause cracks in the films called stress cracking indicating the importance of high vacuum system in sputtering process38. This also reduces collisions with residual gas molecule in the movement of atoms39 from the target to substrate, producing highly uniform thin films. Other than that, step 2.2.2 in the protocol is important to ensure continuous sputtering by dissipating heat through heat transfer with water from the cooling system. This method employs high voltage and electric current which ultimately manifests as target heating. Poor heat dissipation may lead to overheating beyond Curie temperature, resulting in failure of the entire sputtering process40. On top of that, it is suggested to gradually increase the RF power during sputtering by 5 W per 10 s intervals until it reaches the desired power before starting the timer. This step is important to avoid cracks on the target due to thermal shock when too much power is supplied in a very short period of time41.
Sputtering is mainly affected by its parameter including sputtering power, deposition time, working pressure, substrate temperature, and target to substrate distance42,43,44,45. Sputtering power influences the deposition rate and thickness of the film. Increasing voltage causes greater deposition rate, consequently increases the thickness of the film44. Study by Sahu et al.46 shows variation in deposition rate resulting from co-sputtering process of Ni and Zr, with different DC power applied to the Zr target. The results indicate that the deposition rate of the Ni-Zr films increases as the DC power supply for Zr increases. Their later study47 investigated the effect of negative substrate bias voltage on the deposition rate. The result shows that the deposition rate gradually decreases with an increase in the substrate bias voltage. This phenomenon can also be seen in the results of this study where Bi2Te3 sputtered with 75 W produces thicker films than Sb2Te3, which was sputtered with much lower RF power at the same deposition time. However, both films were successfully deposited indicating the RF power exceeds the threshold voltage of each target and can be used in other studies depending on desired thickness.
According to the protocol, this method does not require melting and evaporation of the target material. This leads to nearly all materials can be deposited regardless of their melting temperature, making it superior to other PVD technologies. RF sputtering used in this study is also more advantageous than DC sputtering in terms of stability. Study by Yaqub et al.48 shows that charge accumulation on the surface of the target causes plasma instabilities which hindered the DC sputtering process. In contrast, RF sputtering plasma tends to defuse throughout the chamber rather than concentrating around the target material creating better stability during deposition. Other than that, RF sputtering prevents charge build up which reduce arcing on the target surface, consequently resulting in better films than DC sputtering49.
Despite having various attractive advantages, RF sputtering requires significantly higher voltage compared to DC sputtering with lower deposition rates48. It is also exposed to the risk of overheating due to high voltage which demands advanced circuitry and additional cooling system as stated in step 2.2.2 in the protocol. Apart from that, RF sputtering sustained plasma at much lower pressure by the alternating current, yet the lack of secondary target causes slower deposition rate. This problem can be mitigated by adding secondary discharge between the target and the substrate in order to increase the ionization fraction of sputtered species24. Yet, all these factors contribute to higher cost that leads to RF sputtering only been used in smaller scale and substrates.
Magnetron sputtering is the core of semiconductor industry, where creating highly insulating oxide films (barrier layer), conductive layer and metal grid are significant for integrated circuit fabrication. Various development have been done intended for energy related application such as energy conversion50, widening the implementation of the presented technique, not only for thermoelectric materials, but also for thin film sensors and photovoltaic thin films. Recently, Lenis et al.51 studied the potential of this technique in the biomedical field by depositing the biocompatible and antibacterial coating of HA-Ag/TiN-Ti which is widely used in surgical prostheses. Study by Wang et al.52 also shows the implementation of this technique in depositing nanostructure tungsten trioxide thin films which has important potential application in smart windows field. In conclusion, this method represents a robust platform for thin film deposition and wide range of applications with the potential of further development.
The authors have nothing to disclose.
The authors would like to acknowledge the financial support from Universiti Kebangsaan Malaysia research grant: UKM-GGPM-2022-069 to carry out this research.
Acetone | Chemiz (M) Sdn. Bhd. | 1910151 | Liquid, Flammable |
Antimony Telluride, Sb2Te3 | China Rare Metal Material Co.,Ltd | C120222-0304 | Diameter 50.8 mm, Thickness 6.35 mm, 99.999% purity |
Bismuth Telluride, Bi2Te3 | China Rare Metal Material Co.,Ltd | CB151208-0501 | Diameter 50.8 mm, Thickness 4.25 mm, 99.999% purity |
Ethanol | Chemiz (M) Sdn. Bhd. | 2007081 | Liquid, Flammable |
Field Emission Scanning Electron Microscope | Zeiss | MERLIN | Equipped with EDX |
Hall effect measurement system | Aseptec Sdn. Bhd. | HMS ECOPIA 3000 | – |
Handheld digital multimeter | Prokits Industries Sdn. Bhd. | 303-150NCS | – |
HMS-3000 | Aseptec Sdn Bhd. | HMS ECOPIA 3000 | Hall effect measurement software |
Linseis_TA | Linseis Messgeräte GmbH | LSR-3 | Linseis thermal analysis software |
Methanol | Chemiz (M) Sdn. Bhd. | 2104071 | Liquid, Flammable |
RF-DC magnetron sputtering | Kurt J. Lesker Company | – | Customized hybrid system |
Seebeck coefficient measurement system | Linseis Messgeräte GmbH | LSR-3 | – |
SmartTiff | Carl Zeiss Microscopy Ltd | – | SEM image thickness measurement software |
Ultrasonic bath | Fisherbrand | FB15055 | – |
UV ozone cleaner | Ossila Ltd | L2002A3-UK | – |