CN114231940A - Method for preparing molybdenum sputtering target material by using molybdenum carbonyl as precursor - Google Patents
Method for preparing molybdenum sputtering target material by using molybdenum carbonyl as precursor Download PDFInfo
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- CN114231940A CN114231940A CN202111495064.XA CN202111495064A CN114231940A CN 114231940 A CN114231940 A CN 114231940A CN 202111495064 A CN202111495064 A CN 202111495064A CN 114231940 A CN114231940 A CN 114231940A
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- molybdenum
- deposition
- sputtering target
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- carbonyl
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/16—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal carbonyl compounds
-
- 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
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
Abstract
The invention provides a method for preparing a molybdenum sputtering target by using molybdenum carbonyl as a precursor, which is characterized by comprising the following steps: firstly, carrying out oil and stain removal treatment on a base material; secondly, putting the base material into a deposition chamber of chemical vapor deposition equipment, vacuumizing to 1-20 Pa, and preheating the base material; step three, taking molybdenum hexacarbonyl particles as raw materials, heating to 40-60 ℃ in the atmosphere of high-purity hydrogen and argon, and gasifying the molybdenum hexacarbonyl particles; step four, introducing the mixed gas in the step three into a deposition chamber; and step five, carrying out thermal decomposition vapor deposition on the molybdenum hexacarbonyl on the substrate material. The method disclosed by the invention controls the flow velocity and the flow direction of the reaction gas, and is beneficial to improving the film forming speed and the film forming quality; by adjusting the deposition time, the material, the shape and the size of the deposition substrate, the molybdenum target materials with different thicknesses, sizes and shapes can be deposited, the deposition temperature is low, the deposition process is simple, and no pollution waste gas is generated.
Description
Technical Field
The invention relates to the field of coating preparation, in particular to a method for preparing a molybdenum sputtering target by using molybdenum carbonyl as a precursor.
Background
The molybdenum has excellent physical and chemical properties, such as high melting point (2610 ℃), high hardness, oxidation resistance, high corrosion resistance and the like, and has wide application prospects in the fields of aerospace, weaponry and the like. Meanwhile, the molybdenum metal has low thermal expansion coefficient, high chemical and thermal stability and good conductivity, and is an ideal material for manufacturing a conductive film on glass. Therefore, the molybdenum thin film is widely used in semiconductor integrated circuits, recording media, flat panel displays, and workpiece surface coatings and thin film transistor liquid crystal displays (TFT-LCDs).
The current preparation methods of the molybdenum sputtering target mainly comprise hot isostatic pressing, Spark Plasma Sintering (SPS), forging, vapor deposition and the like. The molybdenum target material prepared by the hot isostatic pressing technology has fine grains and uniform tissues, but has the limitations of high requirements on raw materials, such as low oxygen content and high powder bulk ratio; in addition, the equipment investment is large, the production efficiency is low, the yield of the target is reduced due to high porosity of the produced target, the production cost of the target is high, and the target specification is limited, so that the application is limited. The disadvantage of SPS technology is that it is limited by the equipment, the specification of the prepared target material is limited, and the maximum size is
Can meet the specification requirements of the molybdenum sputtering target material used in the semiconductor industry, but can not meet the requirements of the LCD industry. The casting method has a coarse structure and a certain porosity, thereby affecting the quality of the sputtered film.
Metal Organic Chemical Vapor Deposition (MOCVD) is a process of depositing a solid deposit on the surface of a base material by reacting on the surface of the base material using a metal organic compound as a source substance. The method has the characteristics of high density of a deposition layer, high deposition speed and stable process, can realize uniform deposition of a film layer on a special-shaped substrate, can realize deposition of a composite film and a gradient film layer, and becomes an important means for material surface modification.
Disclosure of Invention
In view of the problems in the background art, the present disclosure is directed to a method for preparing a molybdenum sputtering target from a molybdenum carbonyl precursor.
In order to achieve the above object, the present disclosure provides a method for preparing a molybdenum sputtering target material by using molybdenum carbonyl as a precursor, comprising the following steps: firstly, carrying out oil and stain removal treatment on a base material; secondly, putting the base material into a deposition chamber of chemical vapor deposition equipment, vacuumizing to 1-20 Pa, and preheating the base material; step three, taking molybdenum hexacarbonyl particles as raw materials, heating to 40-60 ℃ in the atmosphere of high-purity hydrogen and argon, and gasifying the molybdenum hexacarbonyl particles; step four, introducing the mixed gas in the step three into a deposition chamber; and step five, carrying out thermal decomposition vapor deposition on the molybdenum hexacarbonyl on the substrate material.
In some embodiments, in step one, the matrix material is selected from Al2O3Ceramic chip, pure copper, tungsten, nickel, titanium, glass.
In some embodiments, in the step one, the oil yielding decontamination method is to clean the oil stain with acetone, then clean with absolute ethyl alcohol, and perform dehydration and drying.
In some embodiments, in the second step, the temperature of the pre-heated substrate material is 300-.
In some embodiments, the purity of the hydrogen and argon in step three is greater than or equal to 99.999%.
In some embodiments, in the fourth step, the gas flow ratio of the mixed gas is 1: 20 to 200: 30 to 300.
In some embodiments, in step five, the thermal decomposition vapor deposition conditions are: the pressure in the deposition chamber is kept at 100-101300Pa, and the deposition temperature is kept at 300-500 ℃.
The beneficial effects of this disclosure are as follows:
the method disclosed by the invention is beneficial to improving the film forming speed and the film forming quality in the sputtering process by controlling the flow speed and the flow direction of the reaction gas; by adjusting the deposition time and the material, shape and size of the deposition substrate, molybdenum targets or molybdenum target blanks with different thicknesses, sizes and shapes can be deposited, the deposition temperature is low, and the deposition process is simple and does not generate polluted waste gas.
Detailed Description
The method for preparing the molybdenum sputtering target material by using the molybdenum carbonyl as the precursor is described in detail below.
The application discloses a method for preparing a molybdenum sputtering target by using molybdenum carbonyl as a precursor, which comprises the following steps: firstly, carrying out oil and stain removal treatment on a base material; secondly, putting the base material into a deposition chamber of chemical vapor deposition equipment, vacuumizing to 1-20 Pa, and preheating the base material; step three, taking molybdenum hexacarbonyl particles as raw materials, heating to 40-60 ℃ in the atmosphere of high-purity hydrogen and argon, and gasifying the molybdenum hexacarbonyl particles; step four, introducing the mixed gas in the step three into a deposition chamber; and step five, carrying out thermal decomposition vapor deposition on the molybdenum hexacarbonyl on the substrate material.
In addition, the shape, the size and the time of the matrix can be adjusted, and high-purity molybdenum targets with different sizes and thicknesses can be produced.
Molybdenum hexacarbonyl is selected in this disclosure because of the low deposition temperature; the product obtained by the reaction does not cause corrosion to equipment.
In step three, the reaction equation involved is Mo (CO)6If molybdenum hexafluoride is used to deposit molybdenum target material, HF generated during the reaction may cause corrosion to the equipment.
In step three, the heating temperature is set to 40-60 ℃, and the temperature range is mainly used for changing the molybdenum hexacarbonyl solid into the molybdenum hexacarbonyl gas. The temperature is too low to become gas; excessive temperatures increase costs.
In some embodiments, in step one, the matrix material is selected from Al2O3Ceramic chip, pure copper, tungsten, nickel, titanium, glass.
In some embodiments, in the step one, the oil yielding decontamination method is to clean the oil stain with acetone, then clean with absolute ethyl alcohol, and perform dehydration and drying.
In some embodiments, in the second step, the temperature of the pre-heated substrate material is 300-. The temperature at which the substrate material is preheated is the reaction temperature, and the reaction gas is introduced into the temperature range to carry out thermal decomposition. If the temperature is too low, molybdenum hexacarbonyl can not be thermally decomposed, and if the temperature is too high, the cost is increased, thereby causing influence on equipment.
In some embodiments, in step three, the purity of the molybdenum carbonyl is more than or equal to 99.9 percent, and the purity of the hydrogen and the argon is more than or equal to 99.999 percent.
In some embodiments, in the fourth step, the gas flow ratio of the mixed gas is 1: 20 to 200: 30 to 300. By controlling the flow rate and the flow direction of the reaction gas, the grain size and the crystal surface orientation of the deposited molybdenum target material can be controlled, so that the sputtering film forming speed and the film forming quality in the sputtering process can be improved.
If the gas flow ratio of the mixed gas is not in the above range, the performance of the metal target material is affected, wherein the hydrogen gas is used for protecting the molybdenum from being oxidized, and the gas ratio corresponds to the partial pressure of the gas, so that the reaction rate is high.
In some embodiments, in step five, the thermal decomposition vapor deposition conditions are: the pressure in the deposition chamber is kept at 100-10000Pa and the deposition temperature is kept at 300-500 ℃. The deposition rate is influenced by too small deposition pressure, and the smaller the pressure is, the smaller the deposition rate is; molybdenum hexacarbonyl with too low deposition temperature can not be thermally decomposed; too high deposition temperature increases cost and affects equipment.
[ test procedures and test results ]
Example 1
Step one, Al with the diameter of 400mm and the thickness of 10mm is added2O3Cleaning oil stains on the ceramic wafer by using acetone, cleaning the ceramic wafer by using absolute ethyl alcohol, and dehydrating and drying the ceramic wafer;
secondly, placing the substrate in a CVD vacuum furnace, vacuumizing to 10Pa, and preheating the substrate to 400 ℃;
step three, taking molybdenum hexacarbonyl particles as raw materials, heating the raw materials to 50 ℃ in the atmosphere of high-purity hydrogen and argon to gasify the raw materials;
step four, introducing the mixed gas of molybdenum hexacarbonyl, hydrogen and argon in the step three into a deposition chamber with the flow ratio of 1: 20: 30;
and step five, carrying out thermal decomposition vapor deposition on the molybdenum hexacarbonyl on the substrate material under the conditions of keeping the pressure of the deposition chamber at 500Pa and the deposition temperature at 400 ℃.
And step six, preparing the finished product of the molybdenum target after thermal annealing treatment and precision machining.
Through detection: the high-purity molybdenum target material or molybdenum target material blank has the dimensions of 400mm in length, 400mm in width, 15mm in thickness and 10.1g/cm in density3The purity is more than 6N.
Example 2
Firstly, cleaning oil stain on pure copper with the diameter of 400mm and the thickness of 10mm by using acetone, cleaning by using absolute ethyl alcohol, and dehydrating and drying;
secondly, placing the substrate in a CVD vacuum furnace, vacuumizing to 10Pa, and preheating the substrate to 400 ℃;
step three, taking molybdenum hexacarbonyl particles as raw materials, heating the raw materials to 50 ℃ in the atmosphere of high-purity hydrogen and argon to gasify the raw materials;
step four, introducing the mixed gas of molybdenum hexacarbonyl, hydrogen and argon in the step three into a deposition chamber with the flow ratio of 1: 20: 30;
and step five, carrying out thermal decomposition vapor deposition on the molybdenum hexacarbonyl on the substrate material under the conditions of keeping the pressure of the deposition chamber at 500Pa and the deposition temperature at 400 ℃.
And step six, preparing the finished product of the molybdenum target after thermal annealing treatment and precision machining.
The high-purity molybdenum target material or molybdenum target material blank has the dimensions of 400mm in length, 400mm in width, 20mm in thickness and 10.15g/cm in density3The purity is more than 6N.
Example 3
Step one, cleaning oil stain on pure copper with the diameter of 500mm and the thickness of 10mm by using acetone, cleaning by using absolute ethyl alcohol, and dehydrating and drying;
secondly, placing the substrate in a CVD vacuum furnace, vacuumizing to 10Pa, and preheating the substrate to 400 ℃;
step three, taking molybdenum hexacarbonyl particles as raw materials, heating the raw materials to 50 ℃ in the atmosphere of high-purity hydrogen and argon to gasify the raw materials;
step four, introducing the mixed gas of molybdenum hexacarbonyl, hydrogen and argon in the step three into a deposition chamber with the flow ratio of 1: 20: 30;
and step five, carrying out thermal decomposition vapor deposition on the molybdenum hexacarbonyl on the substrate material under the conditions that the pressure of a deposition chamber is kept at 500Pa and the deposition temperature is kept at 450 ℃.
And step six, preparing the finished product of the molybdenum target after thermal annealing treatment and precision machining.
The high-purity molybdenum target or molybdenum target blank has the dimensions of 400mm in length, 400mm in width, 25mm in thickness and 10.18g/cm in density3The purity is more than 6N.
The above-disclosed features are not intended to limit the scope of practice of the present disclosure, and therefore, all equivalent variations that are described in the claims of the present disclosure are intended to be included within the scope of the claims of the present disclosure.
Claims (7)
1. A method for preparing a molybdenum sputtering target by using molybdenum carbonyl as a precursor is characterized by comprising the following steps:
firstly, carrying out oil and stain removal treatment on a base material;
secondly, putting the base material into a deposition chamber of chemical vapor deposition equipment, vacuumizing to 1-20 Pa, and preheating the base material;
step three, taking molybdenum hexacarbonyl particles as raw materials, heating to 40-60 ℃ in the atmosphere of high-purity hydrogen and argon, and gasifying the molybdenum hexacarbonyl particles;
step four, introducing the mixed gas in the step three into a deposition chamber;
and step five, carrying out thermal decomposition vapor deposition on the molybdenum hexacarbonyl on the substrate material.
2. The method for preparing molybdenum sputtering target material with molybdenum carbonyl as precursor according to claim 1,
in step one, the matrix material is selected from Al2O3Ceramic chip, pure copper, tungsten, nickel, titanium, glass.
3. The method for preparing molybdenum sputtering target material with molybdenum carbonyl as precursor according to claim 1,
in the first step, the oil-yielding decontamination method comprises the steps of firstly cleaning oil stains by using acetone, then cleaning by using absolute ethyl alcohol, and dehydrating and drying.
4. The method for preparing molybdenum sputtering target material with molybdenum carbonyl as precursor according to claim 1,
in the second step, the temperature of the preheated substrate material is 300-500 ℃.
5. The method for preparing molybdenum sputtering target material with molybdenum carbonyl as precursor according to claim 1,
in the third step, the purity of the hydrogen and the argon is more than or equal to 99.999 percent.
6. The method for preparing molybdenum sputtering target material with molybdenum carbonyl as precursor according to claim 1,
in the fourth step, the gas flow ratio of the mixed gas is that the flow ratio of the molybdenum hexacarbonyl to the hydrogen to the argon is 1: 20-200: 30-300.
7. The method for preparing molybdenum sputtering target material with molybdenum carbonyl as precursor according to claim 1,
in step five, the thermal decomposition vapor deposition conditions are: the pressure in the deposition chamber is kept at 100-101300Pa, and the deposition temperature is kept at 300-500 ℃.
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| CN202111495064.XA CN114231940A (en) | 2021-12-08 | 2021-12-08 | Method for preparing molybdenum sputtering target material by using molybdenum carbonyl as precursor |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999061679A1 (en) * | 1998-05-28 | 1999-12-02 | Sputtering Materials, Inc. | Target for pvd and similar processes |
| EP1862563A2 (en) * | 2006-06-02 | 2007-12-05 | Würth Solar GmbH & Co. KG | Sputter deposition of molybdenum layers |
| WO2020131614A1 (en) * | 2018-12-19 | 2020-06-25 | Entegris, Inc. | Methods for depositing a tungsten or molybdenum layer in the presence of a reducing co-reactant |
| CN112840063A (en) * | 2018-10-10 | 2021-05-25 | 恩特格里斯公司 | Method for depositing tungsten film or molybdenum film |
| CN113755815A (en) * | 2021-09-10 | 2021-12-07 | 安徽光智科技有限公司 | Substrate pretreatment method and preparation method of diamond film |
-
2021
- 2021-12-08 CN CN202111495064.XA patent/CN114231940A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999061679A1 (en) * | 1998-05-28 | 1999-12-02 | Sputtering Materials, Inc. | Target for pvd and similar processes |
| EP1862563A2 (en) * | 2006-06-02 | 2007-12-05 | Würth Solar GmbH & Co. KG | Sputter deposition of molybdenum layers |
| CN112840063A (en) * | 2018-10-10 | 2021-05-25 | 恩特格里斯公司 | Method for depositing tungsten film or molybdenum film |
| WO2020131614A1 (en) * | 2018-12-19 | 2020-06-25 | Entegris, Inc. | Methods for depositing a tungsten or molybdenum layer in the presence of a reducing co-reactant |
| CN113755815A (en) * | 2021-09-10 | 2021-12-07 | 安徽光智科技有限公司 | Substrate pretreatment method and preparation method of diamond film |
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