CN115747744B - Gallium indium oxide film and preparation method thereof - Google Patents
Gallium indium oxide film and preparation method thereof Download PDFInfo
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- CN115747744B CN115747744B CN202310015543.XA CN202310015543A CN115747744B CN 115747744 B CN115747744 B CN 115747744B CN 202310015543 A CN202310015543 A CN 202310015543A CN 115747744 B CN115747744 B CN 115747744B
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Abstract
The invention belongs to the technical field of semiconductor material preparation, and particularly relates to a gallium indium oxide film and a preparation method thereof. The method comprises the following steps: 1) Forming a gallium-indium alloy layer on the surface of the solid metal target; 2) Sputtering the gallium-indium alloy layer on the surface of the solid metal target material in the step 1) by utilizing a magnetron sputtering method, and depositing a film on the substrate; 3) And (3) carrying out annealing treatment on the film obtained in the step (2) in an oxygen-containing atmosphere to obtain the gallium indium oxide film. The preparation method successfully prepares the gallium indium oxide film with excellent performance by a magnetron sputtering method, fills the blank in the field, and has low cost and simple process flow.
Description
Technical Field
The invention belongs to the technical field of semiconductor material preparation, and particularly relates to a gallium indium oxide film and a preparation method thereof.
Background
Since the 50 s of the 20 th century, semiconductor materials have been widely used in today's electronic information technology, particularly in device applications such as computer microprocessors, solar cells, power amplifiers, and the like. The traditional semiconductor material is difficult to be used for high-frequency, high-mobility and high-power devices due to the characteristics of low breakdown field strength and small forbidden bandwidth.
The broad sense of liquid metal refers to metal simple substances and alloys which are in liquid state below 660 ℃, and more commonly used liquid metals are metals which are in liquid state near room temperature, such as gallium or alloys thereof with melting point below 30 ℃, or materials which can be in liquid state in a slightly higher temperature range, such as 40 ℃ to 200 ℃, such as bismuth indium tin zinc and the like. In recent years, with the development of a series of significant researches, the application value of liquid metal is becoming more and more important.
Oxides of the components in the liquid metal may be used as semiconductor materials, for example: gallium oxide (Ga) 2 O 3 ) Indium oxide (In) 2 O 3 ) Tin oxide (SnO) 2 ) Etc. at high levelThe power device field has wide application prospect. The existing preparation methods of liquid metal oxide mainly comprise a chemical deposition method, a sol-gel method, a magnetron sputtering method and the like.
The sol-gel method is easy to introduce impurities, pollutes the environment, has poor adhesion force between the liquid metal oxide film prepared by the chemical vapor deposition method and the matrix, is easy to fall off, and the magnetron sputtering method can overcome the defects of the previous method.
Magnetron sputtering is one type of physical vapor deposition (Physical Vapor Deposition, PVD). The magnetron sputtering technology can be used for preparing multiple materials such as metal, semiconductor, insulator and the like, and has the advantages of simple equipment, easy control, large coating area, strong adhesive force and the like. In the simple way, the magnetron sputtering is to make the electron bound by the closed magnetic field to make spiral motion around the target surface in the orthogonal electromagnetic field, and the argon gas continuously impacts the working gas in the motion process to ionize a large amount of argon ions, the argon ions are accelerated to bombard the target material under the action of the electric field, and the sputtered target atomic ions (or molecules) are deposited on the substrate to form a film. The magnetron sputtering method is used for preparing the liquid metal oxide film, but a part of liquid metal such as gallium indium alloy has a low melting point or is liquid at normal temperature, and cannot be directly used as a target for sputtering, so that a process for preparing the gallium indium oxide film by the magnetron sputtering method needs to be explored.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the gallium indium oxide film and the preparation method thereof, and the gallium indium oxide film is successfully prepared by a magnetron sputtering method, so that the blank in the field is filled, and the preparation method has the advantages of low cost and simple process flow.
Specifically, the invention firstly provides a preparation method of a gallium indium oxide film, which comprises the following steps:
1) Forming a gallium-indium alloy layer on the surface of the solid metal target;
2) Sputtering the gallium-indium alloy layer on the surface of the solid metal target material in the step 1) by utilizing a magnetron sputtering method, and depositing a film on the substrate;
3) And (3) carrying out annealing treatment on the film obtained in the step (2) in an oxygen-containing atmosphere to obtain the gallium indium oxide film.
According to the invention, the gallium indium alloy is combined with common solid metal targets such as copper, iron and zinc targets to obtain the solid metal target with the surface attached with the gallium indium alloy, the solid metal target is used for magnetron sputtering, and the gallium indium oxide film with excellent performance can be prepared by controlling the whole magnetron sputtering process, such as carrier gas, target base distance, sputtering power and the like and combining with an annealing process at a specific temperature.
Preferably, in step 1), the gallium indium alloy layer is formed by impregnating the surface of the solid metal target material with a liquid gallium indium alloy under an acidic condition.
Preferably, in step 1), the mass fraction of gallium in the gallium-indium alloy is 20% -80%.
Preferably, in step 2), the carrier gas of the magnetron sputtering method is a mixture of argon and oxygen, wherein the flow rate of the argon is 20-40sccm, and the flow rate of the oxygen is 0.2-4sccm. Under the above-mentioned argon and oxygen flow, the film forming quality of gallium indium oxide is optimal, wherein the argon flow is too high, then causes the sputtering atom to collide too many times before reaching the substrate, thus lose a lot of energy, the migration ability is limited after reaching the substrate, the crystallization quality is bad, the argon flow is too low, then gas ionization can be difficult, the effect of sputtering glow starting is difficult to take place.
Preferably, in the step 2), the target base distance of the magnetron sputtering method is 15-30mm. The invention discovers that aiming at gallium indium alloy, the effect of the target base distance is optimal, the target base distance is higher than 30mm, the number of times of collision of sputtered atoms reaching a substrate is excessive, the energy loss is large, the nucleation and growth of a film are not facilitated, the deposition rate is reduced, however, if the target base distance is lower than 15mm, the film is bombarded by charged particles, and the deposition rate is too fast, so that the density of various defects in the film is increased.
Preferably, in the step 2), the sputtering power of the magnetron sputtering method is 50-100W. When the sputtering power is lower than 50W, the deposition rate is low, and the energy of sputtered atoms reaching the substrate is also low; when the sputtering power is higher than 100W, the energy of sputtered particles can be increased, but the deposition rate is too high, and the film formation quality of gallium indium oxide is affected.
Preferably, in step 2), the sputtering time of the magnetron sputtering method is 5 to 60min, more preferably 15 to 30min.
Preferably, in step 2), the temperature of the substrate is 25-400 ℃.
Preferably, in step 3), the oxygen-containing atmosphere is oxygen. The present inventors have found that the use of an oxygen-containing atmosphere as described above facilitates further oxidation of the film to form a stable crystal structure.
Preferably, in step 3), the annealing treatment is performed at a temperature of 200-1000 ℃, more preferably 650-750 ℃; the annealing treatment time is 3-6 hours, preferably 4 hours. Experiments show that the crystallinity of the obtained gallium indium oxide film can be obviously improved by annealing for 3-6 hours at 650-750 ℃.
The invention also provides a gallium indium oxide film, which is prepared by the preparation method.
The invention has the beneficial effects that:
according to the invention, the gallium indium alloy is combined with common solid metal targets such as copper, iron and zinc targets to obtain the solid metal target with the gallium indium alloy attached on the surface, and then the gallium indium oxide film prepared by combining a specific magnetron sputtering method with an annealing process is high in crystallinity and light transmittance, excellent in performance, low in cost and simple in process flow.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are needed in the description of the prior art in the embodiments are briefly described below, it being obvious that the drawings in the following description are some embodiments of the invention and that other drawings may be obtained from these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a SEM image before annealing for preparing an indium gallium oxide film according to example 1 of the present invention.
Fig. 2 is an SEM image after annealing for preparing an indium gallium oxide film according to example 1 of the present invention.
Fig. 3 is an XRD pattern after annealing after preparing an indium gallium oxide film according to example 1 of the present invention.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. All reagents or instrumentation are conventional products available for purchase by regular vendors, not noted to the manufacturer.
Example 1
The preparation method of the gallium indium oxide film comprises the following steps:
1. immersing a copper substrate in hydrochloric acid to be in contact with the liquid metal gallium indium alloy, so that the liquid metal gallium indium alloy is immersed on the copper substrate to prepare a liquid metal target;
2. sputtering the gallium indium alloy layer on the surface of the copper substrate in the step 1 by utilizing a magnetron sputtering method, depositing a film on the substrate, wherein the film plating condition is that the argon flow is 30sccm, the oxygen flow is 0.3sccm, the target base distance is 30mm, the substrate temperature is 25 ℃, the sputtering power is 50W, and the sputtering time is 30min, so that a film SEM image is shown in figure 1;
3. after the film is prepared, the film is annealed for 4 hours in an oxygen environment at 700 ℃ in a muffle furnace, and an SEM image of the processed film is shown in fig. 2. XRD analysis was performed on the annealed film, and the XRD pattern was shown in FIG. 3.
As can be seen from SEM images before and after annealing of fig. 1-2, the thin film state before annealing is sheet-like and has no obvious grain structure; the annealed film structure gradually changes into a stacked structure, and obvious particles can be seen, which indicates that the annealing significantly increases the crystallinity of the film. As can be seen from the XRD pattern of fig. 3, intensity peaks of Ga2O3, gaInO3, and (Ga, in) O3 appear In the pattern, indicating that the components In the film are liquid metal oxides (one or a mixture of the three); siO2 is present because the substrate from which the film is made is a silicon wafer.
The above examples are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the claims of the present invention without departing from the spirit of the design of the present invention.
Claims (6)
1. The preparation method of the gallium indium oxide film is characterized by comprising the following steps of:
1) Forming a gallium-indium alloy layer on the surface of the solid metal target;
2) Sputtering the gallium-indium alloy layer on the surface of the solid metal target material in the step 1) by utilizing a magnetron sputtering method, and depositing a film on the substrate;
3) Annealing the film obtained in the step 2) in an oxygen-containing atmosphere to obtain a gallium indium oxide film;
in the step 1), under an acidic condition, the gallium-indium alloy layer is formed by soaking the surface of a solid metal target material with liquid gallium-indium alloy;
in the step 2), the temperature of the substrate is 25-400 ℃;
in the step 3), the temperature of the annealing treatment is 200-1000 ℃; the annealing treatment time is 3-6h.
2. The method for preparing a gallium indium oxide film according to claim 1, wherein in step 1), the mass fraction of gallium in the gallium indium alloy is 20% -80%.
3. The method for preparing a gallium indium oxide film according to claim 1 or 2, wherein in the step 2), the carrier gas of the magnetron sputtering method is a mixed gas of argon and oxygen, wherein the flow rate of the argon is 20-40sccm, and the flow rate of the oxygen is 0.2-4sccm.
4. The method for producing a gallium indium oxide thin film according to claim 1 or 2, wherein in the step 2), the target base distance of the magnetron sputtering method is 15 to 30mm.
5. The method for producing a gallium indium oxide thin film according to claim 1 or 2, wherein in step 2), the sputtering power of the magnetron sputtering method is 50 to 100W;
the sputtering time of the magnetron sputtering method is 5-60min.
6. The method for producing a gallium indium oxide thin film according to claim 1 or 2, wherein in the step 3), the oxygen-containing atmosphere is oxygen.
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| WO2010003947A1 (en) * | 2008-07-08 | 2010-01-14 | Bekaert Advanced Coatings | A method to manufacture an oxide sputter target comprising a first and second phase |
| JP2010238770A (en) * | 2009-03-30 | 2010-10-21 | Nippon Mining & Metals Co Ltd | Oxide thin film, and method of manufacturing the same |
| CN104178721A (en) * | 2013-05-22 | 2014-12-03 | 中国科学院理化技术研究所 | Device for directly manufacturing conductive film at room temperature and method thereof |
| CN106449816A (en) * | 2016-09-22 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Preparation method for copper-indium-gallium-selenide thin film |
| CN109763109A (en) * | 2019-03-04 | 2019-05-17 | 中国科学院理化技术研究所 | A kind of liquid metal target and its method for preparing alloy film |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010003947A1 (en) * | 2008-07-08 | 2010-01-14 | Bekaert Advanced Coatings | A method to manufacture an oxide sputter target comprising a first and second phase |
| JP2010238770A (en) * | 2009-03-30 | 2010-10-21 | Nippon Mining & Metals Co Ltd | Oxide thin film, and method of manufacturing the same |
| CN104178721A (en) * | 2013-05-22 | 2014-12-03 | 中国科学院理化技术研究所 | Device for directly manufacturing conductive film at room temperature and method thereof |
| CN106449816A (en) * | 2016-09-22 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Preparation method for copper-indium-gallium-selenide thin film |
| CN109763109A (en) * | 2019-03-04 | 2019-05-17 | 中国科学院理化技术研究所 | A kind of liquid metal target and its method for preparing alloy film |
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| 透明导电氧化物薄膜的研究现状及展望;李家亮;姜洪义;牛金叶;邹科;;现代技术陶瓷(第01期);第53-57页 * |
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