TWI841064B - Device and method for spraying perovskite film - Google Patents

Abstract

A device for spraying a perovskite film includes a chamber, a carrier, an XY axis moving platform, an ultrasonic spraying system, a feeding device, an auxiliary airflow element, and a heating device. The chamber has a spraying space. The carrier is disposed in the spraying space to carry a substrate. The XY axis moving platform is disposed in the spraying space above the substrate. The ultrasonic spraying system is disposed above the XY axis moving platform. The ultrasonic spraying system ultrasonically oscillates a perovskite precursor solution to spray plural perovskite precursor droplets in the spraying space. The feeding device is connected to the ultrasonic spraying system to supply the perovskite precursor solution to the ultrasonic spraying system. The auxiliary airflow element is adjacent to the ultrasonic spray system and sprays an airflow to blow the perovskite precursor droplets to a surface of the substrate. The heating device heats perovskite precursor droplets.

Description

Calcium-titanium film spraying device and spraying method

The present disclosure relates to a technology for manufacturing a perovskite film, and more particularly to a spraying device and a spraying method for the perovskite film.

Calcium-titanium materials are made of a mixture of organic and inorganic substances. The general chemical formula of calcium-titanium materials can be represented by ABX ₃ , where A represents organic cations, such as HC(NH ₂ ) ²⁺ and CH ₃ NH ³⁺ , B represents metal cations, such as Pb ²⁺ , Ge ²⁺ , and Sn ²⁺ , and X represents monovalent anions, such as halogen anions.

Calcium-titanium material is a direct bandgap semiconductor material with extremely high luminescence efficiency and carrier mobility, and has good absorption capacity for visible light and a wide absorption range. Therefore, calcium-titanium thin films are often used as the active layer of solar cells. Calcium-titanium material can generate high short-circuit current, which makes solar cells have high open-circuit voltage, so calcium-titanium solar cells have good photoelectric conversion efficiency.

At present, the production of calcium-titanium ore mostly uses the scraper coating method, the rotary coating method, and the vacuum deposition method. However, the scraper coating method and the rotary coating method will waste too much calcium-titanium ore precursor solution, the coating area is limited, and the film uniformity is poor, resulting in increased process costs, and it cannot be applied to large-area processes, making it difficult to achieve commercialization. In addition, although the vacuum deposition method can produce a highly uniform calcium-titanium ore film, the deposition area is also quite limited.

Therefore, a technology for manufacturing calcium-titanium thin films is urgently needed to improve the shortcomings of the conventional methods for manufacturing calcium-titanium thin films.

One of the purposes of the present disclosure is to provide a calcium-titanium film spraying device and a spraying method, wherein the ultrasonic spraying system can effectively atomize the calcium-titanium precursor solution into droplets of small particle size, and the auxiliary airflow element can provide airflow to coat these droplets on the surface of the substrate, and the XY axis moving platform can drive the ultrasonic nozzle to move over the surface of the entire substrate. Therefore, not only can the calcium-titanium film be sprayed over a large area, but also the uniformity and grain size of the calcium-titanium film can be improved, and the waste of calcium-titanium can be greatly reduced, effectively reducing the process cost.

Another object of the present disclosure is to provide a spraying device and a spraying method for a calcium-titanium thin film, wherein the cavity can block the external environment, and the spraying space of the cavity can be in a closed state during spraying. Therefore, the instability of the calcium-titanium precursor spray caused by ultrasonic vibration due to external air flow field interference can be avoided, and the problem of film discontinuity and film grain nucleation can be avoided. Therefore, the application of the present disclosure can achieve a high-quality calcium-titanium thin film with low defects.

According to the above-mentioned purpose of the present disclosure, a calcium-titanium thin film spraying device is proposed. This calcium-titanium thin film spraying device includes a chamber, a carrier, an XY axis moving platform, an ultrasonic spraying system, a feeding device, an auxiliary airflow element, and a heating device. The chamber has a spraying space. The carrier is disposed in the spraying space and is configured to carry a substrate. The XY axis moving platform is disposed in the spraying space and is located above the substrate. The XY axis moving platform can move on the XY plane. The ultrasonic spraying system is disposed on the XY axis moving platform. The ultrasonic spraying system is configured to ultrasonically vibrate the calcium-titanium precursor solution to form a plurality of calcium-titanium precursor droplets, and to spray the calcium-titanium precursor droplets in a spraying space. The feeding device is connected to the ultrasonic spraying system and is configured to supply the calcium-titanium precursor solution to the ultrasonic spraying system. The auxiliary airflow element is adjacent to the ultrasonic spraying system and is configured to spray airflow to blow the calcium-titanium precursor droplets toward the surface of the substrate. The heating device is configured to heat the calcium-titanium precursor droplets on the surface of the substrate.

According to an embodiment of the present disclosure, the cavity further has an exhaust port configured to exhaust excess gas in the cavity.

According to one embodiment of the present disclosure, the ultrasonic spray coating system includes an ultrasonic spray head, an ultrasonic oscillator, and a power supply. The ultrasonic spray head is connected to the XY axis moving platform and can be driven by the XY axis moving platform. The ultrasonic oscillator is disposed on the ultrasonic spray head and is configured to vibrate the ultrasonic spray head. The power supply is electrically connected to the ultrasonic oscillator to provide power to the ultrasonic oscillator.

According to one embodiment of the present disclosure, the feeding device comprises an injection pump.

According to an embodiment of the present disclosure, the above-mentioned calcium titanium thin film spray coating device further includes an adjustment mechanism. The adjustment mechanism is arranged in the XY axis moving platform, and the ultrasonic nozzle is arranged at one end of the adjustment mechanism. The adjustment mechanism is configured to drive the ultrasonic nozzle to move along the Z axis direction to adjust the distance between the ultrasonic nozzle and the substrate.

According to the above-mentioned purpose of the present disclosure, a method for spraying a calcium-titanium thin film is also proposed. In this method, a substrate is loaded into a spraying space of a cavity, wherein the spraying space is in a closed state. A calcium-titanium precursor solution is supplied to an ultrasonic nozzle in the spraying space. The calcium-titanium precursor solution is subjected to an atomization step by using the ultrasonic nozzle to generate a plurality of calcium-titanium precursor droplets. When performing the atomization step, the ultrasonic nozzle is moved in an XY plane. A spraying process is performed to use an airflow to blow the calcium-titanium precursor droplets toward and coat the surface of the substrate. The calcium-titanium precursor droplets on the surface of the substrate are heated to form a calcium-titanium film from the calcium-titanium precursor droplets.

According to one embodiment of the present disclosure, when the above-mentioned spraying space is in a closed state, the spraying space is filled with nitrogen, and the water and oxygen in the spraying space are less than 5 ppm.

According to an embodiment of the present disclosure, the atomization step further includes using a power supply to supply power to the ultrasonic oscillator so that the ultrasonic oscillator vibrates the ultrasonic nozzle. The power of the power supply is 0.1 watt to 10 watts.

According to one embodiment of the present disclosure, the moving speed of the ultrasonic nozzle is 1 mm/s to 50 mm/s.

According to one embodiment of the present disclosure, the distance between the ultrasonic nozzle and the substrate is 5 cm to 20 cm.

According to one embodiment of the present disclosure, the heating treatment further includes controlling the heating temperature to be 25°C to 100°C.

The following is a detailed discussion of the embodiments of the present disclosure. However, it is understood that the embodiments provide many applicable concepts that can be implemented in a variety of specific contexts. The embodiments discussed and disclosed are for illustration only and are not intended to limit the scope of the present disclosure. All embodiments of the present disclosure disclose a variety of different features, but these features can be implemented separately or in combination as needed.

In addition, the terms "first", "second", etc. used herein do not specifically refer to order or sequence, but are only used to distinguish between elements or operations described with the same technical terms. In addition, the spatial relationship between two elements described in the present disclosure is applicable not only to the orientations shown in the drawings, but also to orientations not shown in the drawings, such as inverted orientations.

Please refer to FIG1 , which is a schematic diagram of a calcium-titanium thin film spraying device according to an embodiment of the present disclosure. The calcium-titanium thin film spraying device 100 mainly includes a chamber 110, a carrier 120, an XY axis moving platform 130, an ultrasonic spraying system 140, a feeding device 150, an auxiliary air flow element 160, and a heating device 170.

The cavity 110 has a spraying space 112 inside for the spraying operation of calcium-titanium ore. The cavity 110 can be a hollow three-dimensional structure with any suitable shape, such as a hollow rectangular body. In some embodiments, when the calcium-titanium ore is sprayed, the spraying space 112 of the cavity 110 is in a closed state. At this time, the spraying space 112 can be filled with nitrogen, and the water and oxygen in the spraying space 112 can be controlled to be less than 5 ppm.

The chamber 110 may have one or more exhaust ports 114. The exhaust ports 114 may exhaust the excess gas in the chamber 110 out of the chamber 110. During spraying, the exhaust ports 114 only exhaust air passively to avoid abnormalities in the air flow field during spraying due to environmental factors. After spraying is completed, nitrogen may be used to purify the spraying space 112 of the chamber 110, and the exhaust ports 114 are in active exhaust mode.

The carrier 120 is disposed in the spraying space 112 of the chamber 110. The carrier 120 can be used to support the substrate 180 to be coated with a calcium titanium thin film. The carrier 120 can have a flat supporting surface 122 to stably support the substrate 180. For example, the carrier 120 can be a flat plate structure.

The XY axis moving platform 130 is disposed in the spraying space 112 and is located above the substrate 180 supported by the stage 120. The XY axis moving platform 130 can move on the XY plane defined by the X axis A1 and the Y axis A2. For example, the X axis A1 and the Y axis A2 can be perpendicular to each other. In addition, the XY plane can be parallel to the horizontal plane.

The ultrasonic spraying system 140 can be used to ultrasonically vibrate the calcium-titanium precursor solution 192 to form a plurality of calcium-titanium precursor droplets 190, and can spray these calcium-titanium precursor droplets 190 in the spraying space 112 of the chamber 110. The ultrasonic spraying system 140 is disposed on the XY axis moving platform 130 and can be driven by the XY axis moving platform 130.

In some embodiments, the ultrasonic spray system 140 includes an ultrasonic nozzle 142, an ultrasonic oscillator 144, and a power supply 146. The ultrasonic nozzle 142 is disposed in the spraying space 112 and is coupled to the XY axis moving platform 130. The XY axis moving platform 130 can drive the ultrasonic nozzle 142 to move on an XY plane above the substrate 180, and can pass through the entire surface 182 of the substrate 180 in a predetermined path. The moving speed of the ultrasonic nozzle 142 can be, for example, about 1 mm/sec to about 50 mm/sec. The ultrasonic oscillator 144 can, for example, oscillate the ultrasonic nozzle 142 in an ultrasonic oscillation manner. The ultrasonic oscillator 144 can be directly mounted on the ultrasonic nozzle 142 to directly vibrate the ultrasonic nozzle 142. The ultrasonic oscillator 144 can also be indirectly connected to the ultrasonic nozzle 142 to indirectly vibrate the ultrasonic nozzle 142 via the intermediate structure. For example, the ultrasonic oscillator 144 can include an ultrasonic generator, a piezoelectric element, and an amplitude transformer. When performing an ultrasonic vibration operation, the ultrasonic generator can first generate an electronic signal of a specific frequency, and this electronic signal can cause the piezoelectric element to generate a mechanical vibration of the same frequency, and then the amplitude transformer can be used to amplify the amplitude of the mechanical vibration. The oscillation frequency of the ultrasonic oscillator 144 may be about 60 kHz to about 120 kHz. The power supply 146 is electrically connected to the ultrasonic oscillator 144 to provide power to the ultrasonic oscillator 144. The power supply 146 may be disposed outside the cavity 110. The power of the power supply 146 may be, for example, about 0.1 watt to about 10 watts.

The calcium titanium thin film spray coating device 100 may further optionally include an adjustment mechanism 200. The adjustment mechanism 200 may be disposed in the XY axis moving platform 130, and the ultrasonic nozzle 142 is disposed at one end of the adjustment mechanism 200. The adjustment mechanism 200 may be moved along the Z axis A3, for example, by rotation. For example, the Z axis A3 may be perpendicular to the X axis A1 and the Y axis A2. The adjustment mechanism 200 may drive the ultrasonic nozzle 142 to move along the Z axis A3, thereby adjusting the distance P between the ultrasonic nozzle 142 and the substrate 180. In some embodiments, the distance P between the ultrasonic nozzle 142 and the substrate 180 can be controlled to be between about 5 cm and about 20 cm by adjusting the mechanism 200 .

The feed device 150 contains a calcium-titanium precursor solution 192. The feed device 150 is connected to the ultrasonic nozzle 142 to continuously supply the calcium-titanium precursor solution 192 to the ultrasonic nozzle 142. The feed device 150 may be, for example, an injection pump. In some embodiments, the rate at which the feed device 150 supplies the calcium-titanium precursor solution may be controlled to be about 0.1 ml/min to about 5 ml/min.

The auxiliary airflow element 160 is disposed adjacent to the ultrasonic nozzle 142. The auxiliary airflow element 160 can spray gas to form an airflow to blow the calcium-titanium precursor droplets 190 sprayed by the ultrasonic nozzle 142 toward the surface 182 of the substrate 180. The gas sprayed by the auxiliary airflow element 160 can be any suitable gas that does not react with the calcium-titanium precursor droplets 190. For example, the gas can include air and/or nitrogen. In the embodiment shown in FIG. 1 , the auxiliary airflow element 160 is an airflow hood, and the auxiliary airflow element 160 surrounds the side of the ultrasonic nozzle 142. A flow channel is formed between the auxiliary air flow element 160 and the side surface of the ultrasonic nozzle 142 , and the gas ejected by the auxiliary air flow element 160 flows out through the flow channel, while driving the calcium-titanium precursor droplets 190 to flow toward the surface 182 of the substrate 180 .

The auxiliary airflow element disclosed in the present invention may have different types. Please refer to FIG. 2, which is a schematic diagram of an ultrasonic nozzle and an auxiliary airflow element of a calcium-titanium thin film spraying device according to another embodiment of the present invention. The ultrasonic nozzle 142a extends generally in a horizontal direction, rather than extending downward like the ultrasonic nozzle 142. Therefore, the nozzle 142a' of the ultrasonic nozzle 142a sprays calcium-titanium precursor droplets generally in a horizontal direction. The auxiliary air flow element 160a is disposed adjacent to the ultrasonic nozzle 142a to blow the calcium-titanium precursor droplets sprayed from the nozzle 142a' of the ultrasonic nozzle 142a toward the surface 182 of the substrate 180 from top to bottom.

Referring again to FIG. 1 , the heating device 170 can be used to heat the calcium-titanium precursor droplets 190 on the surface 182 of the substrate 180. By heating the calcium-titanium precursor droplets 190, the solvent in the calcium-titanium precursor droplets 190 can be evaporated, so that the calcium-titanium precursor droplets 190 form a calcium-titanium film and crystallize on the surface 182 of the substrate 180. In the embodiment shown in FIG. 1 , the heating device 170 is directly disposed on the bottom surface of the carrier 120 and in contact with the carrier 120. The heating device 170 heats the substrate 180 on the carrier 120 and the calcium-titanium precursor droplet 190 thereon through the carrier 120 by direct heat transfer. The heating device 170 can uniformly control the temperature of the carrier 120. In some exemplary embodiments, the temperature of the heated carrier 120 is set at 50°C. When the temperature uniformity of the carrier 120 is measured by a thermal imager, the temperature non-uniformity of the carrier 120 is ≤±2°C under an area of 1600 ^cm2 .

In other embodiments, a non-contact heating device such as an irradiation device may be used to heat the calcium-titanium precursor droplets 190 on the surface 182 of the substrate 180, wherein the heating device is not in contact with the carrier 120. For example, the calcium-titanium precursor droplets 190 may be heated by irradiating the surface 182 of the substrate 180 from above using an infrared irradiation device.

In some embodiments, the effective spraying area of the calcium-titanium film spraying device 100 is 1600 cm ² . The ultrasonic spraying system 140 is used to effectively atomize the calcium-titanium precursor solution 192 into calcium-titanium precursor droplets 190 of small particle size, and then the auxiliary air flow element 160 is used to supply airflow to coat these calcium-titanium precursor droplets 190 on the surface 182 of the substrate 180, and the XY axis moving platform 130 is used to drive the ultrasonic nozzle 142 to move over the surface 182 of the entire substrate 180. In addition, the cavity 110 can block the external environment, and can avoid the instability of the calcium-titanium precursor spray caused by the vibration of the ultrasonic nozzle 142 due to the interference of the external air flow field, thereby avoiding the problem of film discontinuity and film grain nucleation. Therefore, the calcium-titanium film spraying device 100 can not only spray the calcium-titanium film on a large area, but also improve the uniformity and grain size of the calcium-titanium film, thereby achieving the effect of improving the quality of the calcium-titanium film.

Please refer to FIG. 3, which is a schematic flow diagram of a method for spraying a calcium-titanium thin film according to an embodiment of the present disclosure. The calcium-titanium thin film spraying device 100 described above can be used to spray and manufacture the calcium-titanium thin film, so please refer to FIG. 1 together. When spraying the calcium-titanium thin film, step 300 can be performed first to load the substrate 180 into the spraying space 112 of the chamber 110, and the substrate 180 can be placed on the supporting surface 122 of the carrier 120. Before the calcium-titanium precursor solution 192 is introduced into the spraying space 112, the spraying space 112 can be placed in a sealed state. In some embodiments, the spraying space 112 may be filled with nitrogen in a closed state, and the water and oxygen in the spraying space 112 may be controlled to be less than about 5 ppm.

In some embodiments, before supplying the calcium-titanium precursor solution 192, the ultrasonic nozzle 142 may be moved along the direction of the Z-axis A3 by, for example, the adjustment mechanism 200 to adjust the distance P between the ultrasonic nozzle 142 and the substrate 180 according to the process requirements. In some exemplary embodiments, the distance P between the ultrasonic nozzle 142 and the substrate 180 is controlled to be about 5 cm to about 20 cm.

Next, step 310 may be performed to supply the calcium-titanium precursor solution 192 to the ultrasonic nozzle 142 located in the spraying space 112 by using, for example, the feeding device 150. In some embodiments, the calcium-titanium precursor solution 192 is synthesized from a calcium-titanium solution and a precursor liquid, wherein the calcium-titanium solution may be methyl lead triiodide (MAPbI ₃ ), and the precursor liquid may be a polar aprotic solvent such as dimethylformamide (DMF) or dimethylsulfoxide (DMSO). The calcium-titanium solution and the precursor liquid may be adjusted according to the required concentration. The rate at which the feeding device 150 supplies the calcium-titanium ore precursor solution 192 can be controlled, for example, at about 0.1 ml/min to about 5 ml/min.

Next, step 320 is performed to atomize the calcium-titanium precursor solution 192 using the ultrasonic nozzle 142, so as to atomize the calcium-titanium precursor solution 192 into a plurality of calcium-titanium precursor droplets 190 of small particle size by ultrasonic vibration. When performing the atomization step, the power supply 146 can first be used to supply power to the ultrasonic oscillator 144, so that the ultrasonic oscillator 144 generates ultrasonic vibration to vibrate the ultrasonic nozzle 142. Applying different vibration powers to the ultrasonic oscillator 144 can achieve different solution atomization effects. In some embodiments, the power of the power supply 146 is controlled to be about 0.1 W to about 10 W. In addition, the vibration frequency of the ultrasonic oscillator 144 can be controlled to be about 60 kHz to about 120 kHz, for example.

When the atomization step of the calcium-titanium precursor solution 192 is performed, step 330 can be performed to simultaneously move the ultrasonic nozzle 142 in the XY plane using, for example, the XY axis moving platform 130. The ultrasonic nozzle 142 can be moved according to a preset path so that the ultrasonic nozzle 142 sweeps across the entire surface 182 of the substrate 180 in a zigzag manner. In some embodiments, the moving speed of the ultrasonic nozzle 142 is controlled to be about 1 mm/sec to about 50 mm/sec. By moving the ultrasonic nozzle 142, the uniformity of the calcium-titanium film generated subsequently can be improved, and the grain size of the calcium-titanium film can be increased.

When the atomization step is performed, step 340 can be performed to perform spraying treatment by using, for example, the auxiliary airflow element 160 to provide airflow, and the calcium-titanium precursor droplets 190 sprayed by the ultrasonic nozzle 142 are blown onto the surface 182 of the substrate 180, so that the calcium-titanium precursor droplets 190 are coated on the surface 182 of the substrate 180. The angle of the airflow sprayed by the auxiliary airflow element 160 can be adjusted according to actual process requirements. In addition, the auxiliary airflow element 160 can also be used to provide multiple airflows in different directions to adjust the spraying range and spraying uniformity of the calcium-titanium precursor droplets 190. In some embodiments, the flow rate of the airflow ejected by the auxiliary airflow element 160 is controlled to be about 10 liters/minute to about 25 liters/minute.

Then, step 350 may be performed to heat the calcium-titanium precursor droplets 190 on the surface 182 of the substrate 180 using, for example, a heating device 170. During the heat treatment, the solvent in the calcium-titanium precursor droplets 190 may be evaporated, so that the calcium-titanium precursor droplets 190 form a calcium-titanium film, and the calcium-titanium film may be further crystallized to increase the grain size of the calcium-titanium film. In some embodiments, the heating temperature may be controlled at about 25° C. to about 100° C. during the heat treatment, so that the temperature of the carrier 120 is about 25° C. to about 100° C.

The following uses comparative examples and embodiments to more specifically illustrate the technical content and efficacy of the embodiments disclosed herein. The comparative examples and embodiments use the same calcium-titanium precursor solution. After spraying, if the calcium-titanium film has obvious defects, the spraying uniformity and density of the calcium-titanium film can be identified by naked eyes; and if the surface of the calcium-titanium film is not obvious, an optical microscope can be used to perform regional inspection of the calcium-titanium film. In addition, an X-ray diffraction instrument is used to measure the crystallinity of the calcium-titanium film. Spectra (a) and (b) of FIG. 4 are X-ray diffraction spectra of the calcium-titanium thin film of the comparative example and the embodiment, respectively.

In the comparative example, the feeding rate of the feeding device is 0.25 ml/min, the power of the ultrasonic oscillator of the ultrasonic spraying system is 3.2 W, the oscillation frequency of the ultrasonic oscillator is 60 kHz, the flow rate of the spraying airflow of the auxiliary airflow element is 19 liters/min, the distance between the ultrasonic nozzle and the substrate is 10 cm, the moving speed of the ultrasonic nozzle is 5 mm/s, the temperature of the carrier is 100°C, and the number of spraying back and forth times is 2 times.

In the embodiment, the feeding rate of the feeding device is adjusted to 0.75 ml/min, the power of the ultrasonic oscillator of the ultrasonic spraying system is 3.2 watts, the oscillation frequency of the ultrasonic oscillator is 60 kHz, the flow rate of the spraying airflow of the auxiliary airflow element is 19 liters/min, the distance between the ultrasonic nozzle and the substrate is 10 cm, the moving speed of the ultrasonic nozzle is 5 mm/sec, the temperature of the carrier is 100°C, and the number of spraying back and forth times is 2 times.

The spraying result of the comparative example shows that the calcium-titanium film formed therein is thinner. After the feeding rate of the feeding device of the embodiment is increased from 0.25 ml/min of the comparative example to 0.75 ml/min, it can be observed with the naked eye that the calcium-titanium film of the embodiment is evenly covered on the surface of the substrate, and there are no holes on the surface of the calcium-titanium film. That is, compared with the calcium-titanium film of the comparative example, the calcium-titanium film of the embodiment is thicker and denser. It is judged that the calcium-titanium film of the comparative example is thinner because the feeding rate of the feeding device is too low.

In addition, according to the X-ray diffraction spectra (a) and (b) of FIG. 4 , it can be seen that the crystallinity of the calcium-titanium thin film of the embodiment is higher than that of the comparative example.

In addition, the calcium-titanium film of the embodiment was subjected to an annealing experiment, and its scanning electron microscope photograph is shown in Figure 5. As can be seen from Figure 5, at an annealing temperature of 100°C and an annealing time of 30 minutes, the calcium-titanium film has a higher nucleation state.

In summary, the ultrasonic spraying system of the calcium-titanium film spraying device disclosed herein can effectively atomize the calcium-titanium precursor solution into droplets of small particle size, and the auxiliary airflow element can provide airflow to coat these droplets on the surface of the substrate, and the XY axis moving platform can drive the ultrasonic spray head to move over the surface of the entire substrate. Therefore, not only can the calcium-titanium film be sprayed over a large area, but also the uniformity and grain size of the calcium-titanium film can be improved, and the waste of calcium-titanium can be greatly reduced, effectively reducing the process cost.

In addition, the cavity of the spraying device for the calcium-titanium thin film disclosed in the present invention can block the external environment, and the spraying space of the cavity can be closed during spraying. Therefore, the instability of the calcium-titanium precursor spray caused by ultrasonic vibration due to the interference of the external air flow field can be avoided, and the problem of film discontinuity and thus film grain nucleation can be avoided. Therefore, the application of the present invention can achieve a high-quality calcium-titanium thin film with low defects.

Furthermore, the heating device of the calcium-titanium film spraying device disclosed in the present invention can control the temperature of the substrate, so that the temperature of the calcium-titanium film formed on the substrate can be stably controlled, and the quality of the calcium-titanium film can be more stable.

Although the present disclosure has been disclosed as above by way of embodiments, it is not intended to limit the present disclosure. Anyone with ordinary knowledge in this technical field may make various changes and modifications without departing from the spirit and scope of the present disclosure. Therefore, the protection scope of the present disclosure shall be subject to the definition of the attached patent application scope.

100: Spraying device 110: Cavity 112: Spraying space 114: Exhaust port 120: Carrier 122: Carrier surface 130: XY axis moving platform 140: Ultrasonic spraying system 142: Ultrasonic nozzle 142a: Ultrasonic nozzle 142a’: Nozzle 144: Ultrasonic oscillator 146: Power supply 150: Feeding device 160: Auxiliary airflow element 160a: Auxiliary airflow element 170: Heating device 180: Substrate 182: Surface 190: Calcium-titanium ore precursor droplets 192: Calcium-titanium ore precursor solution 200: Adjustment mechanism 300: Step 310: Step 320: Step 330: Step 340: Step 350: Step A1: X axis A2: Y axis A3: Z axis P: Pitch (a): Graph (b): Graph

The following detailed description in conjunction with the attached drawings will provide a better understanding of the present disclosure. It should be noted that, in accordance with standard industry practice, the features are not drawn to scale. In fact, the dimensions of the features may be increased or decreased at will to make the discussion clearer. [Figure 1] is a schematic diagram of a spraying device for a calcium-titanium film according to one embodiment of the present disclosure. [Figure 2] is a schematic diagram of an ultrasonic nozzle and an auxiliary air flow element of a spraying device for a calcium-titanium film according to another embodiment of the present disclosure. [Figure 3] is a schematic diagram of a process of a spraying method for a calcium-titanium film according to one embodiment of the present disclosure. [Figure 4] is an X-ray diffraction (XRD) spectrum of the calcium-titanium film of the embodiment and the comparative example of the present disclosure. [Figure 5] is a scanning electron microscope photo of the calcium-titanium film of the embodiment of the present disclosure.

Domestic storage information (please note in the order of storage institution, date, and number) None Foreign storage information (please note in the order of storage country, institution, date, and number) None

100: Spraying device

110: Cavity

112: Spraying space

114: Exhaust port

120: Carrier

122: Loading surface

130: XY axis moving platform

140: Ultrasonic spraying system

142: Ultrasonic nozzle

144: Ultrasonic Oscillator

146: Power supply

150: Feeding device

160: Auxiliary airflow element

170: Heating device

180: Substrate

182: Surface

190: Calcium-titanium ore precursor droplets

192: Calcium-titanium ore precursor solution

200: Adjustment mechanism

A1:X axis

A2:Y axis

A3:Z axis

P: Pitch

Claims (11)

A calcium-titanium thin film spraying device comprises: a chamber having a spraying space; a carrier disposed in the spraying space and configured to carry a substrate; an XY axis moving platform disposed in the spraying space and above the substrate, wherein the XY axis moving platform can move on an XY plane; an ultrasonic spraying system disposed on the XY axis moving platform and configured to perform an ultrasonic vibration on a calcium-titanium precursor solution to form a plurality of calcium-titanium precursor droplets, and spray the calcium-titanium precursor droplets in the spraying space. Titanium precursor droplets; a feeding device connected to the ultrasonic spraying system and configured to supply the calcium-titanium precursor solution to the ultrasonic spraying system; an auxiliary airflow element, disposed in the spraying space and outside the ultrasonic spraying system, and configured to spray an airflow to blow the calcium-titanium precursor droplets toward a surface of the substrate after the ultrasonic spraying system sprays the calcium-titanium precursor droplets; and a heating device, configured to perform a heating treatment on the calcium-titanium precursor droplets on the surface of the substrate. The calcium-titanium thin film spraying device as described in claim 1, wherein the chamber further has an exhaust port, and the exhaust port is configured to exhaust excess gas in the chamber. The spray coating device of calcium-titanium thin film as described in claim 1, wherein the ultrasonic spray coating system comprises: an ultrasonic nozzle, which is connected to the XY axis moving platform and can be driven by the XY axis moving platform; an ultrasonic oscillator, which is disposed on the ultrasonic nozzle and configured to vibrate the ultrasonic nozzle; and a power supply, which is electrically connected to the ultrasonic oscillator to provide the ultrasonic oscillator with power. The calcium-titanium thin film spray coating device as described in claim 3 further includes an adjustment mechanism, wherein the adjustment mechanism is arranged in the XY axis moving platform, and the ultrasonic nozzle is arranged at one end of the adjustment mechanism, and the adjustment mechanism is configured to drive the ultrasonic nozzle to move along a Z axis direction to adjust a distance between the ultrasonic nozzle and the substrate. A calcium-titanium film spraying device as described in claim 1, wherein the feed device comprises an injection pump. A method for spraying a calcium-titanium thin film comprises: loading a substrate into a spraying space of a chamber, wherein the spraying space is in a closed state; supplying a calcium-titanium precursor solution to an ultrasonic nozzle in the spraying space; performing an atomization step on the calcium-titanium precursor solution by using the ultrasonic nozzle to generate a plurality of calcium-titanium precursor droplets and spraying the calcium-titanium precursor droplets in the spraying space; During the atomization step, the ultrasonic nozzle is moved on an XY plane; a spray coating process is performed to blow the calcium-titanium precursor droplets onto a surface of a substrate using an air flow after the ultrasonic nozzle sprays the calcium-titanium precursor droplets; and a heat treatment is performed on the calcium-titanium precursor droplets on the surface of the substrate so that the calcium-titanium precursor droplets form a calcium-titanium film. The method for spraying calcium-titanium thin film as described in claim 6, wherein when the spraying space is in the closed state, the spraying space is filled with nitrogen, and the water and oxygen in the spraying space are less than 5 ppm. The method for spraying a calcium-titanium thin film as described in claim 6, wherein the atomization step further includes using a power supply to supply power to an ultrasonic oscillator so that the ultrasonic oscillator vibrates the ultrasonic nozzle, wherein a power of the power supply is 0.1 watt to 10 watts. A method for spraying a calcium-titanium thin film as described in claim 6, wherein a moving speed of the ultrasonic nozzle is 1 mm/s to 50 mm/s. A method for spraying a calcium-titanium thin film as described in claim 6, wherein the distance between the ultrasonic nozzle and the substrate is 5 cm to 20 cm. The method for spraying a calcium-titanium film as described in claim 6, wherein the heat treatment further includes controlling a heating temperature to be 25°C to 100°C.