阅读说明：本技术 一种高比例非晶相ZnO薄膜的快速制备方法 (Method for rapidly preparing high-proportion amorphous phase ZnO film ) 是由 许志武 陈姝 李政玮 马钟玮 闫久春 于 2021-08-27 设计创作，主要内容包括：一种高比例非晶相ZnO薄膜的快速制备方法,本发明涉及ZnO薄膜制备领域。本发明要解决现有方法难以快速形成高比例非晶相ZnO薄膜的技术问题。方法：将AlN陶瓷和Sn9Zn金属块打磨光滑,清洗；将Sn9Zn金属块加热融化形成金属液；加载超声进行表面浸润处理；冷却；二次加热；清洗、风干。本发明将一种化学性质稳定的难润湿陶瓷AlN作为基体,把它浸润到最常见的含Zn低温Sn9Zn共晶金属中。本发明方法中无有毒化学物质的参与,绿色环保。本发明用于光电器件制备领域。(The invention discloses a rapid preparation method of a high-proportion amorphous phase ZnO film, and relates to the field of ZnO film preparation. The invention aims to solve the technical problem that the existing method is difficult to rapidly form a high-proportion amorphous phase ZnO film. The method comprises the following steps: polishing and cleaning AlN ceramic and a Sn9Zn metal block; heating and melting the Sn9Zn metal block to form molten metal; loading ultrasound for surface infiltration treatment; cooling; secondary heating; and (5) cleaning and air drying. The invention takes ceramic AlN which is stable in chemical property and difficult to wet as a matrix, and soaks the ceramic AlN into the most common eutectic metal containing Zn and low-temperature Sn9 Zn. The method of the invention has no toxic chemical substances, and is green and environment-friendly. The invention is used in the field of photoelectric device preparation.)

1. A rapid preparation method of a high-proportion amorphous phase ZnO film is characterized by comprising the following steps:

firstly, polishing AlN ceramic and a Sn9Zn metal block on SiC abrasive paper, and then carrying out ultrasonic cleaning by adopting a cleaning agent;

secondly, placing the Sn9Zn metal block processed in the step one into a TC 4 mold, heating the TC 4 mold by using a heating table, and melting the Sn9Zn metal block to form molten metal;

thirdly, putting the AlN ceramic processed in the first step into the metal liquid formed in the second step, loading ultrasonic waves to carry out surface infiltration treatment, and forming an amorphous ZnO layer on the surface of the AlN ceramic;

taking out the AlN ceramic treated in the step three, and naturally cooling in an atmospheric environment;

fifthly, heating the AlN ceramic cooled in the step four, controlling the heating temperature to be 200-205 ℃, and keeping the heating time for 1-2 min; then, washing by adopting silicone oil; naturally cooling to room temperature in the atmosphere after washing;

sixthly, putting the AlN ceramic treated in the step five into absolute ethyl alcohol for cleaning, and then naturally drying to finish the preparation.

2. The method for rapidly preparing a high proportion of amorphous ZnO film according to claim 1, wherein the SiC sandpaper of step one is type # 800.

3. The method for rapidly preparing a high proportion amorphous phase ZnO film according to claim 1, wherein the cleaning agent in the first step is absolute ethyl alcohol.

4. The method for rapidly preparing a high-proportion amorphous phase ZnO film according to claim 1, wherein in the step one, the ultrasonic cleaning is carried out, the ultrasonic power is controlled to be 50W, and the cleaning time is 5-6 min.

5. The method according to claim 1, wherein the ultrasonic cleaning in step one is performed by using an ultrasonic cleaner.

6. The method according to claim 1, wherein the TC 4 mold in the second step is a titanium alloy mold, one side of the titanium alloy mold is an ultrasonic loading table, and the other side of the titanium alloy mold is a molten metal bath.

7. The method according to claim 1, wherein the heating temperature in step two is set to 230-235 ℃.

8. The method for rapidly preparing the high-proportion amorphous phase ZnO film according to claim 1, wherein the power of the loading ultrasound in the third step is 1000W, and the loading time is 30-35 s.

9. The method according to claim 1, wherein the step five heating is carried out by heating AlN ceramic with a heating table.

10. The method for rapidly preparing a high proportion amorphous phase ZnO film according to claim 1, wherein the temperature of the silicone oil in the fifth step is 200-220 ℃.

Technical Field

The invention relates to the field of ZnO film preparation.

Background

The zinc oxide (ZnO) film is used as a wide-bandgap third-generation semiconductor film material, has small dielectric constant, high transparency and excellent photoelectric property, and is easy to form integration with various semiconductor materials, so the zinc oxide film has great application prospect in the field of photoelectric devices, such as liquid crystal displays, thin film transistors, light emitting diode diodes and the like. And the Zn element has rich reserves on the earth, low raw material cost and good economic benefit.

Compared with a polycrystalline ZnO film, the amorphous ZnO film has higher carrier fluidity due to lack of barrier effect of grain boundary, but ZnO has strong crystallization capacity, and the molecular dynamics calculation is adopted in the literature (Physical review B,2019,99(1):014202.1-014202.11), and the result shows that when the cooling speed reaches 10¹²When K/s is higher, ZnO can form an amorphous thin layer, so that the preparation of an amorphous ZnO film has severe conditions. Many documents (Thin Solid Films,2006,515: 2717-2721; Nature,2004,432(7016):488-492, etc.) report that other elements are often required to be doped to prevent crystallization during the preparation of an amorphous Thin layer of ZnO, so as to obtain a ZnO-rich Thin layer, but this necessarily introduces some impurities; patent CN 103073048A adopts a chemical deposition method to obtain an amorphous ZnO film, but the method has a tedious process, the experimental time is several tens of hours, which greatly reduces the experimental efficiency, and toxic chemicals such as toluene are required in the experimental process.

Disclosure of Invention

The invention provides a rapid preparation method of a high-proportion amorphous phase ZnO film, aiming at solving the problem that the existing method is difficult to rapidly form the high-proportion amorphous phase ZnO film.

A rapid preparation method of a high-proportion amorphous phase ZnO film specifically comprises the following steps:

firstly, polishing AlN ceramic and a Sn9Zn metal block on SiC abrasive paper, and then carrying out ultrasonic cleaning by adopting a cleaning agent;

secondly, placing the Sn9Zn metal block processed in the step one into a TC 4 mold, heating the TC 4 mold by using a heating table, and melting the Sn9Zn metal block to form molten metal;

thirdly, putting the AlN ceramic processed in the first step into the metal liquid formed in the second step, loading ultrasonic waves to carry out surface infiltration treatment, and forming an amorphous ZnO layer on the surface of the AlN ceramic;

taking out the AlN ceramic treated in the step three, and naturally cooling in an atmospheric environment;

fifthly, heating the AlN ceramic cooled in the step four, controlling the heating temperature to be 200-205 ℃, and keeping the heating time for 1-2 min; then, washing by adopting silicone oil; naturally cooling to room temperature in the atmosphere after washing;

sixthly, putting the AlN ceramic treated in the step five into absolute ethyl alcohol for cleaning, and then naturally drying to finish the preparation.

Furthermore, the power of ultrasonic loading in the third step is 1000W, and the loading time is 30-35 s.

Further, the heating temperature in the second step is set to be 230-235 ℃.

And step one, cleaning in an ultrasonic cleaner to remove impurities on the surface of the ceramic material, oxide films on the surface of the metal and the like and prevent adverse effects on the subsequent infiltration process.

And the TC 4 die in the step two is a titanium alloy die, one side of the titanium alloy die is an ultrasonic loading platform, the size of the ultrasonic loading platform is 40mm multiplied by 3mm, one side of the titanium alloy die is a molten metal pool, the size of the outer side of the titanium alloy die is 40mm multiplied by 5mm, and the size of the pool is 30mm multiplied by 3 mm.

Further, the temperature of the silicone oil in the fifth step is 200-220 ℃.

Step three, under the assistance of ultrasound, the liquid Sn9Zn wets the AlN ceramic. Because the infiltration is carried out in the atmospheric environment, enough O atoms can be dissolved in the liquid metal, Zn in the Sn9Zn metal can be gathered on the surface of the AlN ceramic and reacts with O, and a high-proportion amorphous ZnO layer with the thickness of tens of nanometers is formed within 30s under the action of the ultrasonic cavitation effect.

After the third step of treatment, the surface of the AlN ceramic has a certain amount of Sn9Zn metal besides the amorphous layer, so that silicone oil with the temperature higher than 200 ℃ and lower than 220 ℃ is used for washing the AlN ceramic to remove the liquid metal on the surface of the AlN ceramic.

The ceramic AlN with stable chemical property and difficult wetting is taken as a matrix, the ceramic AlN is soaked in the most common eutectic metal containing Zn and Sn9Zn at low temperature, the activity of Zn element is higher than that of Sn, the movement to the surface of AlN is easy, the operation is carried out in the atmospheric environment, and sufficient O element exists in the eutectic liquid, thereby providing sufficient material basis for the formation of a ZnO amorphous thin layer.

ZnO has strong crystallization ability and needs up to 10¹²The cooling rate of K/s is higher than that of the amorphous phase, which imposes severe requirements on heating and cooling in the preparation process. The invention meets the requirement of cooling speed by means of ultrasonic cavitation effect. Under the excitation of ultrasonic wave, the liquid metal produces positive and negative alternative sound pressure change, the tiny gas core in the liquid continuously shrinks and grows along with the positive and negative alternation of the sound pressure, finally the liquid collapses unstably, according to the state equation PV ═ nRT, when the collapse moment of the cavitation bubble, the volume V sharply shrinks, the temperature T in the bubble increases, the instantaneous temperature can reach 10⁵K above, but the surrounding of the cavitation bubble is liquid metal (230 ℃) with low temperature, so that the liquid heated when the bubble collapses in the nearest vicinity of the bubble wall is rapidly cooled, and the cooling speed can reach 10 DEG¹²K/s or more, thereby satisfying the temperature change condition for the formation of ZnO amorphous; the most common low-temperature eutectic Sn9Zn metal containing Zn is selected, the activity of Zn element is greater than that of Sn metal, and the active metal is easy to move to a bonding interface, so that Zn is enriched on the surface of AlN ceramic; since the infiltration process is performed in an atmospheric environment, a sufficient amount of the O element is dissolved in the liquid metal. Therefore, at a lower temperature of 230 ℃ and within a shorter time of 30s, a high proportion of amorphous ZnO thin layer can be prepared.

The invention has the beneficial effects that:

1. the invention adopts common Zn-containing low-temperature eutectic Sn9Zn metal as a wetting material, and the treatment temperature is low.

2. Compared with the process of preparing the amorphous ZnO film by a chemical deposition method, the method can form a high-proportion amorphous layer with the thickness of dozens of nanometers in 30s, and the preparation efficiency is high. The microstructure, diffraction morphology and composition line scanning results of the ZnO thin layer obtained by the method are shown in fig. 2 and fig. 3, only few diffraction spots can be seen from the diffraction morphology, an amorphous diffraction pattern is presented on the whole, the line scanning results show that Zn and O in the thin layer are enriched, and further amplification shows that the thin layer is mainly an amorphous phase and only a small part of crystals exist, so that the ZnO thin film is a high-proportion amorphous phase ZnO thin film.

3. The method of the invention has no toxic chemical substances, and is green and environment-friendly.

4. The matrix material can also be a material which is difficult to wet and has stable chemical properties except AlN, and the matrix mainly plays a role of providing position support for the formation of ZnO, so the selection range of the matrix is wide.

The invention is used in the field of photoelectric device preparation.

Drawings

FIG. 1 is a schematic view of the surface immersion treatment according to a third step of the embodiment, in which 1 represents AlN ceramic, 2 represents molten metal, 3 represents TC 4 mold, 4 represents an ultrasonic transducer, 5 represents a heating stage, and 6 represents a heating pipe;

FIG. 2(a) is a TEM image of an amorphous ZnO thin film prepared in the first example, FIG. 2(b) is a partially enlarged view, and FIG. 2(c) is a diffraction pattern;

FIG. 3 is a graph showing the analysis of the components scanned along the line scan position of FIG. 2 (a).

Detailed Description

The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.

The first embodiment is as follows: the embodiment provides a rapid preparation method of a high-proportion amorphous phase ZnO film, which comprises the following steps:

firstly, polishing AlN ceramic and a Sn9Zn metal block on SiC abrasive paper, and then carrying out ultrasonic cleaning by adopting a cleaning agent;

secondly, placing the Sn9Zn metal block processed in the step one into a TC 4 mold, heating the TC 4 mold by using a heating table, and melting the Sn9Zn metal block to form molten metal;

thirdly, putting the AlN ceramic processed in the first step into the metal liquid formed in the second step, loading ultrasonic waves to carry out surface infiltration treatment, and forming an amorphous ZnO layer on the surface of the AlN ceramic;

taking out the AlN ceramic treated in the step three, and naturally cooling in an atmospheric environment;

fifthly, heating the AlN ceramic cooled in the step four, controlling the heating temperature to be 200-205 ℃, and keeping the heating time for 1-2 min; then, washing by adopting silicone oil; naturally cooling to room temperature in the atmosphere after washing;

sixthly, putting the AlN ceramic treated in the step five into absolute ethyl alcohol for cleaning, and then naturally drying to finish the preparation.

The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the type of the SiC sand paper in the first step is # 800. The rest is the same as the first embodiment.

The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: step one, the cleaning agent is absolute ethyl alcohol. The other is the same as in the first or second embodiment.

The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: step one, ultrasonic cleaning is carried out, wherein the ultrasonic power is controlled to be 50W, and the cleaning time is 5-6 min. The others are the same as in one of the first to third embodiments.

The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: step one, the ultrasonic cleaning adopts an ultrasonic cleaner. The other is the same as one of the first to fourth embodiments.

The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and step two, the TC 4 die is a titanium alloy die, one side of the titanium alloy die is an ultrasonic loading platform, and the other side of the titanium alloy die is a molten metal pool. The other is the same as one of the first to fifth embodiments.

The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and step two, the heating temperature is set to be 230-235 ℃. The other is the same as one of the first to sixth embodiments.

The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: and thirdly, loading ultrasound with the power of 1000W for 30-35 s. The other is the same as one of the first to seventh embodiments.

The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: and step five, heating is carried out on the AlN ceramic by adopting a heating table. The rest is the same as the first to eighth embodiments.

The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and fifthly, controlling the temperature of the silicone oil to be 200-220 ℃. The other is the same as one of the first to ninth embodiments.

The following examples were used to demonstrate the beneficial effects of the present invention:

the first embodiment is as follows:

the embodiment of the invention relates to a method for rapidly preparing a high-proportion amorphous phase ZnO film, which is characterized by comprising the following steps of:

firstly, polishing AlN ceramic and a Sn9Zn metal block on #800 SiC abrasive paper, and then carrying out ultrasonic cleaning in an ultrasonic cleaner by adopting absolute ethyl alcohol as a cleaning agent, wherein the ultrasonic power is controlled to be 50W, and the cleaning time is 5 min; the size of the AlN ceramic is 10mm multiplied by 3 mm;

secondly, placing the Sn9Zn metal block processed in the step one into a TC 4 mold, heating the TC 4 mold by using a heating table, setting the heating temperature to be 230 ℃, and melting the Sn9Zn metal block to form molten metal;

thirdly, putting the AlN ceramic processed in the first step into the metal liquid formed in the second step, loading ultrasound for surface infiltration treatment, controlling the ultrasound power to be 1000W and the loading time to be 30s, and forming an amorphous ZnO layer on the surface of the AlN ceramic;

taking the AlN ceramic treated in the step three out, and naturally cooling to room temperature in an atmospheric environment;

fifthly, heating the AlN ceramic cooled in the step four, controlling the heating temperature to be 200 ℃, and keeping the temperature for 1 min; then, washing by adopting silicone oil with the temperature of 200-220 ℃; naturally cooling to room temperature in the atmosphere after washing;

sixthly, putting the AlN ceramic treated in the step five into absolute ethyl alcohol for cleaning, and then naturally drying to finish the preparation.

The amorphous phase ZnO film obtained by the invention is detected and analyzed to obtain the scanning results of the microstructure, the diffraction appearance and the composition line shown in figures 2 and 3, only a few diffraction spots can be seen from the diffraction appearance, the amorphous diffraction pattern is presented on the whole, the line scanning result shows that Zn and O in the thin layer are enriched, and the further amplification shows that the thin layer is mainly amorphous phase and only a small part of crystals exist, so that the amorphous phase ZnO film is a high-proportion amorphous phase ZnO film.