*Article* **On-Substrate Joule E**ff**ect Heating by Printed Micro-Heater for the Preparation of ZnO Semiconductor Thin Film**

### **Van-Thai Tran <sup>1</sup> , Yuefan Wei <sup>2</sup> and Hejun Du 1,\***


Received: 13 April 2020; Accepted: 9 May 2020; Published: 10 May 2020

**Abstract:** Fabrication of printed electronic devices along with other parts such as supporting structures is a major problem in modern additive fabrication. Solution-based inkjet printing of metal oxide semiconductor usually requires a heat treatment step to facilitate the formation of target material. The employment of external furnace introduces additional complexity in the fabrication scheme, which is supposed to be simplified by the additive manufacturing process. This work presents the fabrication and utilization of micro-heater on the same thermal resistive substrate with the printed precursor pattern to facilitate the formation of zinc oxide (ZnO) semiconductor. The ultraviolet (UV) photodetector fabricated by the proposed scheme was successfully demonstrated. The performance characterization of the printed devices shows that increasing input heating power can effectively improve the electrical properties owing to a better formation of ZnO. The proposed approach using the on-substrate heating element could be useful for the additive manufacturing of functional material by eliminating the necessity of external heating equipment, and it allows in-situ annealing for the printed semiconductor. Hence, the integration of the printed electronic device with printing processes of other materials could be made possible.

**Keywords:** inkjet printing; zinc oxide; heat treatment; micro-heater; semiconductor

### **1. Introduction**

Exploration of inkjet printing for the fabrication of electronic devices has recently become a trendy research topic due to the remarkable advantages of the digital-additive fabrication such as saving material and time, high resolution, and compatibility with different materials [1,2]. These advantages of inkjet printing have been widely employed for the fabrication of semiconductor devices [3,4]. Thanks to its outstanding features and abundance, zinc oxide (ZnO) has attracted considerable attention and effort in the additive fabrication of electronics devices such as solar cells [5,6], photodetectors [3,7], and transistors [8,9]. Additive manufacturing of inorganic material from a precursor compound usually requires a heat treatment step in order to convert precursors to the required material [10,11]. However, the annealing process using an external furnace might restrain the progress of 3D printed integrative devices because of the added complexity of the fabrication system.

Low temperature processing of metal oxide has been intensively studied via different approaches, such as ultraviolet (UV) annealing [12,13] and laser sintering [14], in order to facilitate the formation of metal oxide by heating effect of high energy light beam, which requires high complexity setup for the processing system. Furthermore, direct use of nanoparticle ink was considered instead of precursor ink [15]. However, added surfactant to keep nanoparticle ink stable might be an issue for electronic

application because it might change the properties of printed material. Alternatively, using local Joule heating to form metal oxide by thermal decomposition of precursor compound is an interesting approach to prepare small-size metal oxide pattern [16].

Joule heating is the phenomenon in which heat is generated from a conductive material when there is an electrical current run through the conductor. The power consumed is proportional to the square of the electrical current and the resistance of the conductor [17]. A micro-heater working on the Joule heating principle possesses advantages such as local heat and optimized energy consumption. Therefore, the resistive heater has been employed in application that requires localized heating and temperature control at small scale, such as activation of gas sensing device [18,19], moisture monitoring [20], and local growth of semiconductor nanostructures [21]. The traditional approach of preparing conductive patterns is using photolithography to deposit and remove certain parts of the conductive film and forming the required shape of the film. As this method has its own drawbacks, such as the high complexity and time-consuming, additive manufacturing could be a promising candidate for fabrication of micro-heaters [22].

In this work, a facile and versatile fabrication process for additive fabrication of semiconductor using inkjet printing and on-substrate heating was proposed. The printed conductive material is further employed for another role, which is the heating element for later processes. Zinc precursor ink is then printed on the same substrate. Eventually, electrical power was applied to the micro-heater to generate heat, which facilitates the decomposition of the zinc salt and the formation of ZnO. Therefore, the necessity for an external bulky furnace is eliminated. The generation of ZnO was examined by the elemental survey of zinc (Zn) and oxygen (O) component in energy-dispersive X-ray spectroscopy (EDS) and the aid of thermogravimetric analysis (TGA). In order to demonstrate the obtained semiconductor film, a UV photodetector application was prepared and characterized. The influence of electrical power during Joule heating to photodetector performance is also evaluated.

### **2. Materials and Methods**

A commercialized Dimatix 2831 inkjet printer (Fujifilm Dimatix, Inc, Santa Clara, CA, USA) was employed in all printing steps described in this work using 10 pL cartridge with 16 nozzles. The silicon/silicon dioxide (Si/SiO2) substrate (Bonda Technology Pte Ltd, Singapore) was cleaned before the printing of silver ink to construct the electrodes and heater. The substrate was cleaned in acetone and rinsed with isopropanol, then it was dried out by a manual air blower.

A commercial silver nanoparticle ink (silver dispersion 736465, Sigma-Aldrich, St. Louis, MO, USA) was employed for the printing of the silver patterns. Detail of the printing step has been discussed in our previous report [23]. The waveform applied to piezoelectric nozzle to jet ink is shown in Figure A1a (Appendix A). Peak firing voltage was set at 19 V. Drop-spacing was set at 40 µm to ensure the continuity of the printed silver line. Single layer was selected for printing of electrodes and four-layers was selected for printing of micro-heater. Cartridge temperature was set at 35 ◦C, however, due to the printer platen temperature was set at 60 ◦C and the close distance of the cartridge and the substrate during printing, the cartridge temperature may rise to about 40 ◦C during printing. The printed pattern was left on the platen of the printer for 10 min for solvent vaporization.

Printed single line of conductive silver features 100 µm in width, and the thickness is about 200 nm as reported in our previous works [23]. The as-printed single line resistance was measured as 15.5 Ω. Due to the Joule heating process using 4-W power, the resistance was reduced to 5.0 Ω as the effect of sintering.

Figure 1 depicts the fabrication of the device using Joule heating. Printed metal patterns, serving as electrical contacts for the sensor as well as the micro-heater, was printed on the first step of the fabrication process (Figure 1a). The micro-heater composes of two contacting pad and a single line of conductive silver serving as a heating resistor. Then, direct current was applied to the micro-heater, which consumes 4-W power and converts it to heat energy for 5 min (Figure 1b). The generated heat promotes the sintering of silver electrodes and improves the bonding to substrate. The power applied

to the micro-heater was manually adjusted by turning the voltage of the direct current (DC) power source when monitoring the current. During the Joule heat treatment, the resistance of the micro-heater changed due to sintering effect which require a careful adjustment of voltage. For example, a 5 W of power was obtained by turning the voltage to 5.0 V while the current reached 1.0 A. source when monitoring the current. During the Joule heat treatment, the resistance of the microheater changed due to sintering effect which require a careful adjustment of voltage. For example, a 5 W of power was obtained by turning the voltage to 5.0 V while the current reached 1.0 A.

**Figure 1.** Fabrication step of the sensor using including printed micro-heater. (**a**) Printing of conductive pattern for the metal contacts and heater. (**b**) Applying direct current (DC) power to the micro-heater to generate heat and sinter silver. (**c**) Deposition of zinc salt ink over the printed electrodes. (**d**) Applying DC power again to the micro-heater to calcinate ZnO. **Figure 1.** Fabrication step of the sensor using including printed micro-heater. (**a**) Printing of conductive pattern for the metal contacts and heater. (**b**) Applying direct current (DC) power to the micro-heater to generate heat and sinter silver. (**c**) Deposition of zinc salt ink over the printed electrodes. (**d**) Applying DC power again to the micro-heater to calcinate ZnO.

A 50 mM zinc precursor solution was formulated by dissolving of zinc acetate dihydrate (Zn(CH3COO)2·2H2O) to ethanol. Another cartridge was used to print the zinc precursor after the replacement of the silver ink cartridge by zinc precursor ink cartridge. A rectangular pattern of the zinc salt solution is printed over the metal contacts, which is nearby the micro-heater (Figure 1c). The beneath substrate was kept heated at a temperature of 60 °C during printing to facilitate the A 50 mM zinc precursor solution was formulated by dissolving of zinc acetate dihydrate (Zn(CH3COO)2·2H2O) to ethanol. Another cartridge was used to print the zinc precursor after the replacement of the silver ink cartridge by zinc precursor ink cartridge. A rectangular pattern of the zinc salt solution is printed over the metal contacts, which is nearby the micro-heater (Figure 1c). The beneath substrate was kept heated at a temperature of 60 ◦C during printing to facilitate the evaporation of the solvent and reduce the spreading of solution over the surface.

evaporation of the solvent and reduce the spreading of solution over the surface. Ten layers of zinc precursor was printed with a designed pattern of 60 pixels by 50 pixels. Zinc precursor ink printing parameters were optimized to ensure the stability during printing. The waveform was given in Figure A1b (Appendix A) with peak voltage at 19 V. The cartridge was kept at room temperature. Drop spacing, defining by the distance of two nearby droplets, was set at Ten layers of zinc precursor was printed with a designed pattern of 60 pixels by 50 pixels. Zinc precursor ink printing parameters were optimized to ensure the stability during printing. The waveform was given in Figure A1b (Appendix A) with peak voltage at 19 V. The cartridge was kept at room temperature. Drop spacing, defining by the distance of two nearby droplets, was set at 10 µm, so that it is necessary to calibrate the cartridge holder angle during printing different materials.

10 μm, so that it is necessary to calibrate the cartridge holder angle during printing different materials. After the printing of the precursor, electrical current was applied to the resistive heater again for 5 min (Figure 1d). Two sets of samples which have 4-W and 5-W applied power were studied along After the printing of the precursor, electrical current was applied to the resistive heater again for 5 min (Figure 1d). Two sets of samples which have 4-W and 5-W applied power were studied along with the samples without the treatment. A thermal camera (NEC F30W, AVIO, Turin, Italy) was employed to measure the temperature of the device during the Joule heating process.

with the samples without the treatment. A thermal camera (NEC F30W, AVIO, Turin, Italy) was employed to measure the temperature of the device during the Joule heating process. Thermogravimetric analysis (TGA) using the equipment TGA Q500 (TA Instruments, New Castle, DE, USA) was utilized for studying the formation of zinc oxide by thermal process. The heating rate we used for TGA is 10 °C/min. Film morphology and elemental study were characterized by field emission–scanning electron microscope (FE–SEM, JOEL 7600F, JEOL Ltd., Tokyo, Japan) and energy dispersive X-ray spectroscopy (EDS) (Oxford Instruments, Abingdon, United Kingdom). In order to characterize the performance of the Joule heating processed sensor, an ultraviolet lightemitting diode which emits 365 nm wavelength was used to illuminate the sensor and measure the photocurrent under dark or lighting condition. The photocurrent was recorded using a source Thermogravimetric analysis (TGA) using the equipment TGA Q500 (TA Instruments, New Castle, DE, USA) was utilized for studying the formation of zinc oxide by thermal process. The heating rate we used for TGA is 10 ◦C/min. Film morphology and elemental study were characterized by field emission–scanning electron microscope (FE–SEM, JOEL 7600F, JEOL Ltd., Tokyo, Japan) and energy dispersive X-ray spectroscopy (EDS) (Oxford Instruments, Abingdon, UK). In order to characterize the performance of the Joule heating processed sensor, an ultraviolet light-emitting diode which emits 365 nm wavelength was used to illuminate the sensor and measure the photocurrent under dark or lighting condition. The photocurrent was recorded using a source metering unit (SMU B2902A, Agilent, Santa Clara, CA, USA).

metering unit (SMU B2902A, Agilent, Santa Clara, CA, USA).

### **3. Results 3. Results 3. Results**
