CN109763109A - A kind of liquid metal target and its method for preparing alloy film - Google Patents
A kind of liquid metal target and its method for preparing alloy film Download PDFInfo
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- CN109763109A CN109763109A CN201910161639.0A CN201910161639A CN109763109A CN 109763109 A CN109763109 A CN 109763109A CN 201910161639 A CN201910161639 A CN 201910161639A CN 109763109 A CN109763109 A CN 109763109A
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Abstract
The present invention relates to sputtering film fields, more particularly to a kind of liquid metal target and its alloy film of preparation, the liquid metal target includes target substrate and the liquid metal target layer for being overlying on the target substrate surface, and the liquid metal is gallium-base alloy, and the target substrate is copper or iron.Liquid metal target preparation process of the present invention is simple, alloy film growth speed is fast when preparing alloy with it, thickness uniform, controllable, it is easy to operate, efficiently convenient, the continuous controllable alloy film film from nanoscale to micro-meter scale thickness can be achieved, conductivity with higher has stronger production applicability.
Description
Technical field
The present invention relates to the preparation fields of alloy film, and in particular to one kind is prepared used in film by magnetron sputtering method
Liquid metal target and its alloy film of preparation.
Background technique
The energy is the problem of world is paid close attention to jointly, and to solve energy crisis, solar power generation becomes an important industry.
CIGS thin film solar battery is the chalcopyrite crystallization being made of four kinds of Cu (copper), In (indium), Ga (gallium) and Se (selenium) elements
Thin-film solar cells, with light absorpting ability is strong, power generation stability is good, high conversion efficiency, generating dutation length on daytime, generated energy
High, production cost is low and many advantages such as the energy recovery period is short, is gradually widely used.For CIGS hull cell
Manufacture for, the preparation of CIGS light absorbing layer is important a ring, and the preparation method of CIGS thin-film mainly has molten at present
Agent thermal method, spray pyrolysis method, ion sintering process, chemical deposition, reactive sputtering, vacuum vapor deposition method etc..Wherein use magnetic control
Selenizing has become mainstream technology of preparing means of the industry to sputtering sedimentation copper and indium gallium (CIG) alloy-layer again.Copper and indium gallium closes
The magnetron sputtering mode of layer gold generally includes following two: the first is using CuGa bianry alloy target and In target cosputtering
Mode, be for second direct sputtering CuInGa ternary alloy three-partalloy target.Usual CuInGa CuGa target using smelting process this
There are ingredient and technique " window " are relatively narrow for kind method；Interphase easy to form, is segregated, and leads to finally formed alloy film not
Uniform cold spraying there are the utilization rate of spraying powder lower (generally 40~60% or so), rotary target material can only be prepared, very
Hardly possible is used for the production of planar targets.Particle cold moudling method smelting temperature is higher to make low melting point (higher than 1084 DEG C of the fusing point of copper)
Indium or gallium volatilization it is serious, cause the alloying component of final particle and designed ingredient to mismatch；Using indium gallium zinc
The method of target material magnetic sputtering prepares IGZO film, and target preparation process is complicated and sputtering uniformity is bad, and then influences film layer
Quality.
In addition, indium gallium zinc IGZO is a kind of novel semiconductor material, there is electronics more higher than amorphous silicon (α-Si)
Mobility.IGZO is used in high performance thin film transistor (TFT) of new generation and is used as channel material, to improve display panel resolution
Rate.High performance thin film transistor (TFT) is not only used on display screen, can also replace the electronics core of traditional based single crystal silicon
Piece.Its preparation process there is a problem of similar with magnetron sputtering C uInGa film.
Summary of the invention
For the prior art the problem of preparing alloy target material and magnetron sputtering alloy film, present invention firstly provides
A kind of liquid metal target, including target substrate and the liquid metal target layer for being overlying on the target substrate surface, the liquid
Metal is gallium-base alloy or gallium, and the target substrate is copper or iron.
Liquid metal is overlying on the surface of copper or iron target substrate and prepares alloy film as target by the present invention, with tradition
CuGa or CuGaIn target is compared, and liquid metal is uniformly distributed on the surface of target substrate in liquid form, in preparation process
It not will form interphase, it is ensured that be formed by the uniformity of alloy film after final sputtering, guarantee the alloying component of final particle
Match with designed ingredient.
Preferably, the liquid metal target layer with a thickness of 0.1~1.0mm.Liquid metal may be implemented in above-mentioned thickness
Layer and guarantees that liquid metal is adhered on target matrix surface for the uniform fold on surface.
Preferably, the gallium-base alloy is gallium-indium alloy.
It is further preferred that the molar percentage of gallium is 20~100%, more preferable 40~60% in the gallium-indium alloy.
Preferably, the impurity content in the simple substance indium and Metallic Gallium is no more than 0.01%
Preferably, liquid metal target of the present invention, is prepared by the following method: by liquid metal and target base
Bottom is placed in acid solution and handles, and the liquid metal is made to be overlying on the surface of the target substrate.
Preferably, the pH of the acid solution handles 1~10min less than 2 under conditions of 20~100 DEG C of temperature；
It is further preferred that the pH of the acid solution is 0~1,1~5min is handled under conditions of 40-80 DEG C of temperature.
It is another object of the present invention to the method that Sustainable use liquid metal target of the present invention prepares alloy film, masters
Wanting improvement is, using liquid metal target of the present invention and copper or zinc as raw material, to prepare alloy film by cosputtering method.
Preferably, copper content is greater than 99.99% in copper target material, and Zn content is greater than 99.99% in zinc target.
Preferably, include the following steps: the liquid metal target and copper target material or by the liquid metal target and
Zinc target, which is placed in physical vapor deposition coating film equipment, carries out plated film by cosputtering method.
Preferably, the liquid metal target plating conditions are as follows: 10~30sccm of argon flow, oxygen flow 0 or 10~
30sccm, target-substrate distance 18-40mm, 15-25 DEG C of base reservoir temperature, sputtering power 40-100W.
The plating conditions of the copper or zinc target are as follows: 10~30sccm of argon flow, 18~40mm of target-substrate distance, base reservoir temperature 15
~25 DEG C, 40~100W of sputtering power.
Preferably, the solid substrate includes but is not limited to one of silicon wafer, glass, copper, molybdenum, PDMS or a variety of；
Further preferably silicon wafer, molybdenum or glass.
As a preferred option, the preparation method of alloy film of the present invention includes the following steps:
1) gallium base fluid state metal targets layer is coated on the surface of target substrate copper or iron, obtains liquid metal target；
2) using the liquid metal target and copper target material or zinc target as raw material, alloy film is prepared by cosputtering method.
The alloy film that the present invention also protects the method for the invention to be prepared；It is preferred that GaInZn film or CuGaIn film.
Preferably, GaInZn alloy film of the present invention is sputtered under oxygen atmosphere, and by oxidation processes, it is excellent
It is selected in 300-800 DEG C of temperature, heat treatment time 2h~12h obtains IGZO film.
Final object of the present invention is that the protection liquid metal alloy film is preparing the application in solar battery；
It is preferred that preparing the application in solar cell light absorption layer.
The invention has the following beneficial effects:
1) it is closed with the prior art using CuGa bianry alloy target and In target cosputtering or directly sputtering CuInGa ternary
Gold target material is compared, liquid metal is overlying on copper or iron target substrate by method of the invention, and liquid metal can after treatment
Spreading wetting is realized in copper or iron matrix, the equally distributed target of liquid can be obtained, and liquid and solid interphase is not present, into
And it can guarantee the uniformity of sputtering caudacoria.
2) liquid metal target preparation process of the present invention is simple, and it is fast to prepare alloy film growth speed using the target,
Thickness uniform, controllable, it is easy to operate, efficiently convenient, it can be achieved that from nanoscale to micro-meter scale thickness continuous controllable alloy film
Film, the film being prepared conductivity with higher have stronger production applicability, are suitable for including CIGS thin film solar energy
Battery, indium gallium spelter coating, gallium oxide coatings, the application such as gallium nitride coating.
Detailed description of the invention
Fig. 1 is 1 liquid metal target figure of embodiment；
Fig. 2 is embodiment 1CuInGa alloy film SEM figure；
Fig. 3 is embodiment 2GaInZn alloy film section SEM figure.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
The present embodiment first relates to a kind of hydraulic pressure metal target, and the target includes target substrate and is overlying on the target base
The gallium-indium alloy target layer of bottom surface, the target substrate are copper.
In the gallium-indium alloy, the molar ratio 50:50 of simple substance indium and Metallic Gallium, the target layer with a thickness of 0.8mm, institute
The impurity content of the simple substance indium and Metallic Gallium stated is no more than 0.01%；
The target is prepared by the following method:
Copper target material substrate and Liquid metal Ga In alloy, being put into pH value is in 0 acid solution, 40 DEG C at a temperature of,
Copper target material surface prepares liquid metal GaIn alloy-layer (see Fig. 1, preparation time 5min), as seen from Figure 1, liquid metal alloy
Layer uniform fold on Copper substrate.
The invention further relates to a kind of liquid metal film, preparation method includes the following steps: to be greater than 99.99% with copper content
Copper target material be raw material, by the liquid metal target and Cu target merging PVD in carry out on silicon wafer cosputtering plate CuInGa
(SEM is shown in Fig. 2).PVD coating process are as follows: the liquid metal target plating conditions are as follows: argon flow 15sccm, oxygen flow
0sccm, target-substrate distance 40mm, 20 DEG C of base reservoir temperature, sputtering power 40W.The plating conditions of the copper target are as follows: argon flow
30sccm, target-substrate distance 18mm, 25 DEG C of base reservoir temperature, sputtering power 100W.
As seen from Figure 2, crystal grain distribution is uniform in the obtained alloy film layer of the method for the invention sputtering, fine and close.
Embodiment 2
The present embodiment first relates to a kind of hydraulic pressure metal target, and the target includes target substrate and is overlying on the target base
The gallium-indium alloy target layer of bottom surface, the target substrate are copper.
In the gallium-indium alloy, the molar ratio 40:60 of simple substance indium and Metallic Gallium, the target layer with a thickness of 0.5mm.Institute
The impurity content of the simple substance indium and Metallic Gallium stated is no more than 0.01%.
The target is prepared by the following method:
Copper target material substrate and Liquid metal Ga In alloy, being put into pH value is in 1 acid solution, at a temperature of 60 DEG C, in copper
Target material surface prepares liquid metal GaIn alloy-layer, preparation time 2min.
Material using Zn content greater than 99.99% will be carried out as zinc target in liquid metal target and Zn target merging PVD
Cosputtering plating GaInZn in silicon wafer substrate (alloy section SEM is shown in Fig. 3).PVD coating process are as follows: the liquid metal target plated film
Condition are as follows: argon flow 20sccm, oxygen flow 30sccm, target-substrate distance 25mm, 20 DEG C of base reservoir temperature, sputtering power 60W.It is described
The plating conditions of zinc target are as follows: argon flow 30sccm, oxygen flow 30sccm, target-substrate distance 20mm, sputter function by 25 DEG C of base reservoir temperature
Rate 80W.
As seen from Figure 3, the GaInZn coating of method of the invention preparation is fine and close, and thickness is uniform.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of liquid metal target, which is characterized in that golden including target substrate and the liquid for being overlying on the target substrate surface
Belong to target layer, the liquid metal is gallium-base alloy or gallium, and the target substrate is copper or iron.
2. liquid metal target according to claim 1, which is characterized in that the liquid metal target layer with a thickness of
0.1~1mm.
3. liquid metal target according to claim 1, which is characterized in that the gallium-base alloy is gallium-indium alloy, described
The molar percentage of gallium is 20~100%, preferably 40~60% in gallium-indium alloy；
It is further preferred that the impurity content in the simple substance indium and Metallic Gallium is no more than 0.01%.
4. described in any item liquid metal targets according to claim 1~3, which is characterized in that be prepared by the following method:
Liquid metal and target substrate are placed in acid solution and are handled, the liquid metal is made to be overlying on the surface of the target substrate.
5. liquid metal target according to claim 4, which is characterized in that the pH of the acid solution is less than 2, in temperature
1~10min is handled under conditions of 20~100 DEG C；
Preferably, the pH of the acid solution is 0~1, and 1~5min is handled under conditions of 40~80 DEG C of temperature.
6. a kind of preparation method of alloy film, which is characterized in that with the described in any item targets of Claims 1 to 5 and copper or zinc
For raw material, alloy film is prepared by cosputtering method.
7. preparation method according to claim 6, which is characterized in that be prepared by the following method: by the liquid gold
Belong to target and copper target material or the liquid metal target and zinc target are placed in physical vapor deposition coating film equipment by splashing altogether
It penetrates method and carries out plated film；
Preferably, the plating conditions of the liquid metal target are as follows: 10~30sccm of argon flow, oxygen flow 0 or 10~
30sccm, 18~40mm of target-substrate distance, 15~25 DEG C of base reservoir temperature, 40~100W of sputtering power；
And/or the plating conditions of the copper or zinc target are as follows: 10~30sccm of argon flow, oxygen flow 0 or 10~
30sccm, 18~40mm of target-substrate distance, 15~25 DEG C of base reservoir temperature, 40~100W of sputtering power.
8. preparation method according to claim 7, which is characterized in that the substrate include but is not limited to silicon wafer, glass,
One of copper, molybdenum, PDMS or a variety of, preferably silicon wafer, molybdenum or glass.
9. the alloy film that any one of claim 6~8 the method is prepared, preferably GaInZn film or CuGaIn alloy film.
10. liquid metal alloy film described in claim 9 is preparing the application in solar battery；It is preferred that in preparation solar-electricity
Application in the light absorbing layer of pond.
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Cited By (3)
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|---|---|---|---|---|
| CN112062147A (en) * | 2020-09-21 | 2020-12-11 | 山东大学 | Low-cost and high-efficiency preparation method of lutetium oxide film |
| CN115504845A (en) * | 2021-06-22 | 2022-12-23 | 中国科学院理化技术研究所 | Liquid metal working medium belt for laser micro-propulsion and preparation method thereof |
| CN115747744A (en) * | 2023-01-06 | 2023-03-07 | 中国科学院理化技术研究所 | Indium gallium oxide film and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062147A (en) * | 2020-09-21 | 2020-12-11 | 山东大学 | Low-cost and high-efficiency preparation method of lutetium oxide film |
| CN112062147B (en) * | 2020-09-21 | 2021-11-09 | 山东大学 | Low-cost and high-efficiency preparation method of lutetium oxide film |
| CN115504845A (en) * | 2021-06-22 | 2022-12-23 | 中国科学院理化技术研究所 | Liquid metal working medium belt for laser micro-propulsion and preparation method thereof |
| CN115504845B (en) * | 2021-06-22 | 2023-10-13 | 中国科学院理化技术研究所 | Liquid metal working medium belt for laser micro-propulsion and preparation method thereof |
| CN115747744A (en) * | 2023-01-06 | 2023-03-07 | 中国科学院理化技术研究所 | Indium gallium oxide film and preparation method thereof |
| CN115747744B (en) * | 2023-01-06 | 2023-04-21 | 中国科学院理化技术研究所 | Gallium indium oxide film and preparation method thereof |
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