CN113293353B - Metal-doped zirconium diboride film and preparation method thereof - Google Patents

Metal-doped zirconium diboride film and preparation method thereof Download PDF

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CN113293353B
CN113293353B CN202110560481.1A CN202110560481A CN113293353B CN 113293353 B CN113293353 B CN 113293353B CN 202110560481 A CN202110560481 A CN 202110560481A CN 113293353 B CN113293353 B CN 113293353B
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孟瑜
弥娟莉
刘明霞
张秀萍
徐可为
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Xian University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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Abstract

The invention provides a metal-doped zirconium diboride film and a preparation method thereof, wherein the film is prepared from a metal target and ZrB 2 The composite target is used as a target material byDeposition of metal element doped ZrB on silicon substrate by magnetron sputtering method 2 A film; the metal element is a metal that is more easily oxidized than Zr and B. The invention adopts the magnetron co-sputtering technology to perform reaction on ZrB 2 Metal elements which are easy to absorb oxygen are introduced into the film, thereby reducing the oxygen pair ZrB 2 The influence of the film makes the Zr-B atomic ratio approach to the stoichiometric ratio, thereby avoiding the formation of ZrO 2 And B 2 O 3 The crystallinity of the film is adjusted, the chemical composition and microstructure of the film are changed, the O content in the film is reduced, the film resistance is reduced, and the controllable preparation of the film component and microstructure is realized.

Description

Metal-doped zirconium diboride film and preparation method thereof
Technical Field
The invention belongs to the technical field of functional film preparation, and particularly relates to a metal-doped zirconium diboride film and a preparation method thereof.
Background
Zirconium diboride has a high melting point (3245 ℃), high hardness (22 GPa), and low thermal expansion coefficient (5.9X 10) -6 ℃ -1 ) And low resistivity (4.6 mu omega cm) and the like, and can be used as a high-temperature structure ceramic material, a thin film material, a composite material, an electrode material and the like. ZrB commonly used 2 The preparation method of the film comprises a Chemical Vapor Deposition (CVD) method and a magnetron sputtering technology. However, zrB prepared by CVD 2 The film has higher resistivity due to higher content of C and O elements, and the internal structure is looser, thereby influencing the service performance of the film. Compared with a CVD method, the magnetron sputtering technology is a deposition method with better application prospect, and has the characteristics of smooth film surface, good bonding force, uniform thickness, compact structure and higher controllability.
But ZrB was prepared during magnetron sputtering 2 In the film process, zr and B both have strong affinity to O atoms, so that the prepared film is easy to oxidize and is more prone to generate ZrO 2 And B 2 O 3 Not ZrB having a stoichiometric ratio 2 And is ZrO 2 And ZrB 2 Has different crystal structures and high resistivity, and obviously influences the electrical characteristics of the zirconium diboride film.
Disclosure of Invention
The invention aims to provide a metal-doped zirconium diboride film and a preparation method thereof, which reduce the film resistance and improve the electrical characteristics.
The invention is realized by the following technical scheme:
a process for preparing the metal doped zirconium diboride film from metal target and ZrB 2 The composite target is used as a target material, and ZrB doped with metal elements is deposited on a silicon substrate by a magnetron sputtering method 2 A film; the metal element is a metal that is more easily oxidized than Zr and B.
Preferably: the metal element is Al or Ta.
Further: the metal elements are Al, a metal target and ZrB 2 The ratio of the sputtering power of the composite target is (30-50): 80.
further: the metal elements are Ta, metal target and ZrB 2 The ratio of the sputtering power of the composite target is (30-50): 100.
preferably: the metal target material adopts radio frequency sputtering, zrB 2 The composite target adopts direct current sputtering or radio frequency sputtering.
Preferably: the silicon substrate is a single-side polished Si (100) substrate.
Preferably: before magnetron sputtering, cleaning and pretreating a silicon substrate: and sequentially placing the silicon substrate in acetone and ethanol for ultrasonic cleaning, and then soaking in an HF solution to remove an oxide layer on the surface of the silicon substrate.
Preferably, the following components: the deposition time is 30-120 min.
The metal-doped zirconium diboride film obtained by the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts the magnetron co-sputtering technology to perform reaction on ZrB 2 Metal elements which are easy to absorb oxygen are introduced into the film, thereby reducing the oxygen pair ZrB 2 The influence of the film makes the atomic ratio of Zr and B approach the stoichiometric ratio and avoids generating ZrO 2 And B 2 O 3 Adjusting the crystallinity of the film, changing the chemical composition and microstructure of the film, reducing the O content in the film, reducing the resistance of the film, and realizing the composition and the microstructure of the filmControllable preparation of microstructure.
Further, by adjusting ZrB 2 And the ratio of the sputtering power of the metal, the atomic ratio of Zr and B in the film can be adjusted, and the chemical composition and the microstructure of the film can be adjusted.
ZrB of the invention 2 The Zr and B atomic ratio in the film approaches to the stoichiometric ratio, the resistivity is low, and the film has better electrical characteristics.
Drawings
FIG. 1 shows an example of undoped ZrB 2 Surface topography of the film.
FIG. 2 shows an example of Al-doped ZrB 2 Surface topography of the film.
FIG. 3 shows an example of Al-doped ZrB 2 XRD pattern of the film.
FIG. 4 shows Ta-doped ZrB in an embodiment of the present invention 2 Surface topography of the film.
FIG. 5 shows Ta-doped ZrB in an embodiment of the invention 2 XRD pattern of the film.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The preparation method comprises the following steps: step 1) carrying out cleaning pretreatment on a Si substrate; specifically, a silicon substrate is sequentially placed in acetone and ethanol for ultrasonic cleaning for 10min, and then is soaked in an HF solution to remove an oxide layer on the surface of the silicon substrate, so that organic pollutants on the surface of the silicon substrate are removed, and the film-substrate binding force is improved; wherein the concentration of the acetone solution is more than 99.9%; the concentration of the ethanol solution is more than 99.9 percent, and finally 5 percent HF solution is used for removing the oxide layer on the surface.
Step 2) preparing a layer of zirconium diboride film doped with metal element (M) on the surface of the cleaned and pretreated Si substrate in a vacuum inert gas atmosphere; specifically, the operation is as follows:
deposition of metallic element doped ZrB on Si (100) substrates using magnetron sputtering equipment 2 Film, the target material is metal target and ZrB 2 The purity of the composite target is 99.95 percent,the metal target adopts radio frequency sputtering, zrB 2 The target material adopts direct current sputtering or radio frequency sputtering. Background vacuum degree of 4.0 × 10 -4 Pa, ar gas flow rate of 80ml/min, sputtering power of the doped metal target of 30-50W 2 The target sputtering power is 60-100W, the substrate bias voltage is 50-150V, the working air pressure is 0.4-2 Pa, and the sputtering time is 30-120 min, so as to obtain the Zr-M-B film.
The thickness of the Zr-M-B film is 20-500nm, and the Zr-M-B film mainly consists of ZrB 2 Compound and metal simple substance or metal oxide.
Examples of metals as Al are as follows:
a metal-doped zirconium diboride film and a preparation method thereof comprise the following steps:
step 1) carrying out cleaning pretreatment on a Si substrate; specifically, a silicon substrate is sequentially placed in acetone and ethanol for ultrasonic cleaning, and then is soaked in an HF solution to remove an oxide layer on the surface of the silicon substrate, so that organic pollutants on the surface of the silicon substrate are removed, and the film-substrate binding force is improved; wherein the concentration of the acetone solution is more than 99.9%; the concentration of the ethanol solution is more than 99.9 percent, and finally 5 percent HF solution is used for removing the oxide layer on the surface.
Step 2) preparing a layer of Al-doped zirconium diboride film on the surface of the cleaned and pretreated Si substrate in a vacuum inert gas atmosphere; specifically, the operation is as follows:
deposition of Al-doped ZrB on Si (100) substrates using a magnetron sputtering apparatus 2 The target material is Al target and ZrB 2 The purity of the composite target is 99.95 percent, and the Al target adopts radio frequency sputtering and ZrB 2 The target is sputtered by direct current. Background vacuum degree of 4.0 × 10 - 4 Pa, ar gas flow rate of 80ml/min, al target sputtering power of 30-50W 2 The target sputtering power is 80W, the substrate bias voltage is 150V, the working air pressure is 0.6Pa, and the sputtering time is 60min, so that the Zr-Al-B film is obtained. The sputtering power of the Al target and the elemental composition of the Zr-Al-B film are shown in Table 1.
TABLE 1 sputtering power of Al target and elemental composition in Zr-Al-B films
Figure BDA0003078770500000041
As can be seen from Table 1, the oxygen content in the Al-doped thin film is reduced, and as the sputtering power of the Al target is increased, the oxygen content is gradually reduced, the Zr/B atomic ratio is gradually increased, and the sputtering power of the Al target is 50, the final value is close to 2.
For the Zr-Al-B thin films prepared in the above examples, the film thickness was 120 to 500nm. When the surface morphology of the film is observed by SEM, as can be seen from FIG. 1, the undoped ZrB 2 The surface of the film is smooth and compact. FIG. 2 shows an Al-doped ZrB 2 The surface topography of the film shows that the particles on the surface of the sample have small size and are uniformly distributed. As can be seen from the XRD spectrum of FIG. 3, the film sample is crystalline and ZrB is formed with the increase of Al sputtering power 2 The peak intensity was reduced, indicating that the Al incorporation caused lattice distortion, and that Al appeared when the Al sputtering power was 50W 2 O 3 The diffraction peak of (1). According to the four-point probe test result, the sheet resistance of the film is between 8.286 and 4.31 omega/\9633andthe film has good electrical property.
Examples of metals as Ta are as follows:
a metal-doped zirconium diboride film and a preparation method thereof comprise the following steps:
step 1) the same as in the above example;
step 2) depositing Ta doped ZrB on a Si (100) substrate using a magnetron sputtering device 2 The target material is Ta target and ZrB 2 The purity of the composite target is 99.95 percent. Background vacuum degree of 4.0 × 10 -4 Pa, ar gas flow rate of 80ml/min, ta target sputtering power of 30, 40, 50W and ZrB respectively 2 The target sputtering power is 100W, radio frequency sputtering is adopted, the substrate bias voltage is 150V, the working air pressure is 0.5Pa, the sputtering time is 30min, zr-Ta-B films with different Ta contents are obtained, and the thickness of the Zr-Ta-B films is 40-100nm. The sputtering power of the Ta target and the elemental composition of the Zr-Ta-B film are shown in Table 2.
TABLE 2 Ta target sputter Power and elemental composition in Zr-Ta-B films
Figure BDA0003078770500000051
As can be seen from Table 2, the oxygen content in the film after Ta doping is reduced, and as the sputtering power of the Ta target is increased, the oxygen content is gradually reduced, the Zr/B atomic ratio is gradually increased, and the sputtering power of the Ta target is 50, and finally approaches to 2.
As shown in FIG. 4, zrB at a Ta sputtering power of 30W 2 SEM picture of film, and ZrB 2 The film is the same, and the surface of the sample is flat and compact. FIG. 5 shows ZrB with different Ta sputtering powers 2 XRD pattern of the film, the Zr-Ta-B film prepared by the method is of a nanocrystalline or microcrystalline structure and mainly consists of Ta (202) crystal grains.

Claims (3)

1. A preparation method of a metal-doped zirconium diboride film is characterized by comprising the following steps: with a metal target and ZrB 2 The composite target is used as a target material, and ZrB doped with metal elements is deposited on a silicon substrate by a magnetron sputtering method 2 A film; the metal element is a metal which is more easily oxidized than Zr and B;
the specific method comprises the following steps: the metal target is an Al target, the metal element is Al, and the Al-doped ZrB is deposited on the Si (100) substrate by utilizing a magnetron sputtering device 2 Film, al target and ZrB 2 The purity of the composite target is 99.95 percent, and the Al target adopts radio frequency sputtering and ZrB 2 The target adopts direct current sputtering; background vacuum degree of 4.0 × 10 -4 Pa, ar gas flow rate of 80ml/min, al target sputtering power of 50W 2 The target sputtering power is 80W, the substrate bias voltage is 150V, the working air pressure is 0.6Pa, and the sputtering time is 60 min;
the resulting Al-doped ZrB 2 The thickness of the film is 120-500 nm; the resulting Al-doped ZrB 2 The atomic percent of Al in the film was 6.71, the atomic percent of oxygen was 5.59, and the Zr/B atomic ratio was 1.98; resulting Al-doped ZrB 2 The sheet resistance of the film is between 8.286 and 4.31 omega/\ 9633for the manufacture of the film.
2. The method of preparing a metal-doped zirconium diboride film according to claim 1, wherein: before magnetron sputtering, cleaning and pretreating a silicon substrate: and sequentially placing the silicon substrate in acetone and ethanol for ultrasonic cleaning, and then soaking in an HF solution to remove an oxide layer on the surface of the silicon substrate.
3. A metal-doped zirconium diboride film obtainable by the process according to any one of claims 1 to 2.
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