CN100415640C - Ultra-fine high-nitrogen tantalum nitride powder and its preparation method - Google Patents
Ultra-fine high-nitrogen tantalum nitride powder and its preparation method Download PDFInfo
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- CN100415640C CN100415640C CNB2005100315854A CN200510031585A CN100415640C CN 100415640 C CN100415640 C CN 100415640C CN B2005100315854 A CNB2005100315854 A CN B2005100315854A CN 200510031585 A CN200510031585 A CN 200510031585A CN 100415640 C CN100415640 C CN 100415640C
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Abstract
The present invention discloses superfine tantalum nitride powder with high nitrogen content and a preparation method thereof. The nitrogen content of tantalum nitride powder is from 6.8 to 7.40%, the total content of impurities is less than 0.0090%, tantalum is used as the rest, and the fisher particle size Fsss is less than 1 um. The present invention has the preparation method 1 that tantalum powder with the low oxygen content which is not more than 0.4% is placed in a common vacuum reactor, evacuation is carried out until the pressure is not higher than 0.1Pa, the temperature is raised to be from 400 to 750 DEG C, nitrogen gas is filled after constant temperature, the temperature is raised to be from 700 to 1200 DEG C, and the constant temperature is maintained under the nitrogen pressure of 0.02 to 0.16Mpa; the present invention has the preparation method 2 that high oxygen tantalum powder whose oxygen content is more than 0.4% and magnesium powder whose weight is 2 to 10% of that of the tantalum powder are mixed and are placed in a common vacuum reactor; evacuation is carried out until the pressure is not higher than 0.1Pa, the temperature is raised to be from 400 to 550 DEG C, the argon gas of high purity is filled after constant temperature, and the temperature is raised to be from 700 to 800 DEG C; after the constant temperature, the argon gas is pumped away, the nitrogen gas is filled, the temperature is raised to be from 950 to 1200 DEG C, and the constant temperature is maintained under the nitrogen pressure of 0.02 to 0.16Mpa; the reaction product of the two preparation methods is cooled to room temperature, is crushed and sieved, is washed with acid to remove impurities, is washed with water and is dried.
Description
Technical field
The present invention relates to tantalum nitride powder and preparation thereof, particularly ultra-fine high-nitrogen tantalum nitride powder and preparation method thereof.
Background technology
The nitrogenize tantalum film has a series of good electric properties, as good thermostability, and lower temperature factor, thereby in semi-conductor, unicircuit, important application is arranged.Tantalum nitride membrane still is that a kind of good diffusion hinders film, in copper and silicon semiconductor junction, spreads in silicon substrate in order to prevent copper atom, hinders material with the nitrogenize tantalum film as diffusion and has a wide range of applications.Simultaneously, tantalum nitride membrane hardness height, chemical stability is good, erosion resistance is strong, heat-resisting and anti-punching performance is strong, makes it industrial very wide application prospect be arranged, and now has been successfully used to make high speed thermal printer head and some corrosion-proof wear-resistant materials on the facsimile recorder.For the application of nitrogenize tantalum film in technical fields such as semi-conductor, unicircuit further expanded, for example it and high specific capacitance tantalum powder are mixed, production has higher interior poly-porosity, the high specific volume of better thermodynamic stability, the solid capacitor of low ESR etc., just require the necessary nitrogen content height of tantalum nitride powder, and its Fisher particle size Fsss must be less than 1um, and the tantalum nitride membrane that makes with this ultra-fine high-nitrogen tantalum nitride powder could satisfy its technical requirements.222～226) etc. (Kenneth Brezinsky.Journal of American CeramicSociety, 2003,86 (2): the people has studied in ebullated bed Akhil Jain, by means of the synthetic Ta of microwave burning
2The N powder, but the total nitrogen content of this product low (theoretical value is 3.74%) can not satisfy above-mentioned technical requirements, and this preparation method's equipment complexity, be difficult for industrialization; H Wiesenberger (W Lengauer, P Ettmayer.ActaMaterials, 1998,651～666) etc. 46 (2): the people studies metal tantalum piece and nitrogen generation nitrogenize situation, think that the generation temperature of tantalum nitride must be more than or equal to 1830 ℃, such high temperature has proposed very high requirement to equipment, and what obtain is the tantalum nitride piece, and the technology and the equipment that are processed into tantalum nitride membrane also must be complicated.
Summary of the invention
It is low to the present invention seeks to overcome the tantalum nitride powder total nitrogen content that above-mentioned prior art exists, or must synthesize by high temperature, and preparation method and equipment complexity thereof, the technical requirements height, be difficult for defectives such as industrialization, a kind of total nitrogen content height is provided, the ultra-fine high-nitrogen tantalum nitride powder of Fisher particle size Fsss＜1um, and utilize the conventional vacuum reaction vessel under lower conventional smelting temperature, to prepare the method for this powder, realize the industrialization of ultra-fine high-nitrogen tantalum nitride powder, satisfy the nitrogenize tantalum film at semi-conductor, further expand the technical requirements and the market requirement of application in the technical fields such as unicircuit.
For realizing goal of the invention, it is 6.8～7.40% that the present invention has prepared nitrogen content by weight percentage, content of impurities＜0.0090%, and surplus is a tantalum, the ultra-fine high-nitrogen tantalum nitride powder of powder Fisher particle size Fsss＜1um.
For preparing this ultra-fine high-nitrogen tantalum nitride powder, the present invention has adopted two kinds of different preparation methods:
The first kind of preparation method who adopts comprises oxygen level≤0.4% with by weight percentage, the hypoxemia tantalum powder of Fisher particle size Fsss＜1um is packed in the conventional vacuum reaction vessel, after being evacuated to pressure≤0.1Pa, be warmed up to 400～750 ℃, constant temperature charges into the high pure nitrogen of purity 〉=99.999% after 1 hour, be warmed up to 700～1200 ℃ again, and the maintenance nitrogen pressure is 0.02～0.16Mpa, constant temperature 3～5 hours, then behind the cool to room temperature with the reaction product fragmentation, sieve, remove impurity through pickling, be washed to the solution pH value again and be the oven dry of neutral back.
The second kind of preparation method who adopts comprises oxygen level＞0.4% with by weight percentage, the hyperoxia tantalum powder of Fisher particle size Fsss＜1um and consumption are that 2～10% magnesium powder thorough mixing of described hyperoxia tantalum grain weight amount is even, in the conventional vacuum of packing into the reaction vessel, after being evacuated to pressure≤0.1Pa, be warmed up to 400～550 ℃, constant temperature charges into the high-purity argon gas of purity 〉=99.999% after 1 hour, be warmed up to 700～800 ℃, constant temperature 2～5 hours, extract argon gas then, charge into the high pure nitrogen of purity 〉=99.999%, be warmed up to 950～1200 ℃ again, and the maintenance nitrogen pressure is 0.02～0.16Mpa, constant temperature 3～5 hours, then behind the cool to room temperature with the reaction product fragmentation, sieve, remove impurity, be washed to the solution pH value again and be the oven dry of neutral back through pickling.
The invention has the advantages that and adopt the conventional vacuum reaction vessel, and temperature of reaction can prepare ultra-fine high-nitrogen tantalum nitride powder below 1200 ℃, save facility investment and energy cost greatly, equipment is simple and reliable, and is easy to operate, is easy to realize suitability for industrialized production.The product that adopts the inventive method preparation proves that with the crystalline structure that the present technique normally used X-ray diffractometer XRD in field (Cu target, K alpha-ray) measures powder the product that obtains is a tantalum nitride; Analyze wherein nitrogen content with oxygen/nitrogen combined measuring instrument again, all more than or equal to 6.8%, reach as high as 7.39% by weight percentage; By the scanning electron microscope sem photo Fisher particle size Fsss＜1um of the high-nitrogen tantalum nitride powder that obtains as can be known, successfully be used in further expanding of semi-conductor, unicircuit and use in the neck city.
Description of drawings
Fig. 1 is the scanning electron microscope sem photo of ultra-fine high-nitrogen tantalum nitride powder of the present invention.
Specific implementation method
The invention will be further described below in conjunction with embodiment and accompanying drawing.
Embodiment 1: with oxygen level is 0.28% (weight percent, following examples are all identical), Fisher particle size Fsss is that the 25kg hypoxemia tantalum powder of 0.84um is packed in the conventional vacuum reaction vessel, be warmed up to 750 ℃ of constant temperature 1 hour after being evacuated to pressure≤0.1Pa, charge into the high pure nitrogen (nitrogen gas purity following examples are all identical) of purity 〉=99.999% again, be warmed up to 1200 ℃ of constant temperature 3 hours, and keep nitrogen pressure at 0.02Mpa, cool to room temperature then.With the reaction product fragmentation, sieve, be 3～5 stoichiometric acid (hydrochloric acid, or sulfuric acid, or nitric acid with equivalent concentration; Following examples are identical) 10L carries out pickling, and be washed to the solution pH value again and be the oven dry of neutral back.To the dust sampling analysis of preparation, its chemical ingredients and weight percent and Fisher particle size see Table 1.
Embodiment 2: the 25kg hypoxemia tantalum powder that oxygen level is 0.40%, Fisher particle size Fsss is 0.80um is packed in the conventional vacuum reaction vessel, be warmed up to 450 ℃ of constant temperature 1 hour after being evacuated to pressure≤0.1Pa, charge into nitrogen again, be warmed up to 700 ℃ of constant temperature 5 hours, and keep nitrogen pressure at 0.16Mpa, cool to room temperature then.With the reaction product fragmentation, sieve, be that 3～5 stoichiometric sour 10L carry out pickling with equivalent concentration, be washed to the solution pH value again and be the oven dry of neutral back.To the dust sampling analysis of preparation, its chemical ingredients and weight percent and Fisher particle size see Table 1.
Embodiment 3: the 25kg hypoxemia tantalum powder that oxygen level is 0.35%, Fisher particle size Fsss is 0.78um is packed in the conventional vacuum reaction vessel, be warmed up to 550 ℃ of constant temperature 1 hour after being evacuated to pressure≤0.1Pa, charge into nitrogen again, be warmed up to 900 ℃ of constant temperature 5 hours, and keep nitrogen pressure at 0.12Mpa, cool to room temperature then.With the reaction product fragmentation, sieve, be that 3～5 stoichiometric sour 10L carry out pickling with equivalent concentration, be washed to the solution pH value again and be the oven dry of neutral back.To the dust sampling analysis of preparation, its chemical ingredients and weight percent and Fisher particle size see Table 1.
Embodiment 4: with oxygen level is 1.20%, Fisher particle size Fsss is that the 25kg hyperoxia tantalum powder of 0.84um and 2.5kg magnesium powder (consumption be described hyperoxia tantalum grain weight amount 10%) thorough mixing is even, in the conventional vacuum of packing into the reaction vessel, be warmed up to 400 ℃ of constant temperature 1 hour after being evacuated to pressure≤0.1Pa, charge into the high-purity argon gas (purity of argon following examples are all identical) of purity 〉=99.999% again, be warmed up to 700～800 ℃ of constant temperature 2 hours, extract argon gas then, charge into nitrogen again, be warmed up to 950 ℃ of constant temperature 5 hours, and keep nitrogen pressure at 0.02Mpa, cool to room temperature then.With the reaction product fragmentation, sieve, be that 3～5 stoichiometric sour 30L carry out pickling with equivalent concentration, be washed to the solution pH value again and be the oven dry of neutral back.To the dust sampling analysis of preparation, its chemical ingredients and weight percent and Fisher particle size see Table 1.
Embodiment 5: oxygen level is 0.6%, Fisher particle size Fsss is 0.80um 25kg hyperoxia tantalum powder and 0.5kg magnesium powder (consumption be described hyperoxia tantalum grain weight amount 2%) thorough mixing is even, in the conventional vacuum of packing into the reaction vessel, be warmed up to 550 ℃ of constant temperature 1 hour after being evacuated to pressure≤0.1Pa, charge into argon gas again, be warmed up to 700～800 ℃ of constant temperature 5 hours, extract argon gas then, charge into nitrogen again, be warmed up to 950 ℃ of constant temperature 5 hours, and keep nitrogen pressure at 0.16Mpa, cool to room temperature then.With the reaction product fragmentation, sieve, be that 3～5 stoichiometric sour 20L carry out pickling with equivalent concentration, be washed to the solution pH value again and be the oven dry of neutral back.To the dust sampling analysis of preparation, its chemical ingredients and weight percent and Fisher particle size see Table 1.
Embodiment 6: oxygen level is 0.67%, Fisher particle size Fsss is 0.66um 20kg hyperoxia tantalum powder and 1kg magnesium powder (consumption be described hyperoxia tantalum grain weight amount 5%) thorough mixing is even, in the conventional vacuum of packing into the reaction vessel, be warmed up to 400 ℃ of constant temperature 1 hour after being evacuated to pressure≤0.1Pa, charge into argon gas again, be warmed up to 700～800 ℃ of constant temperature 3 hours, extract argon gas then, charge into nitrogen again, be warmed up to 1200 ℃ of constant temperature 3 hours, and keep nitrogen pressure at 0.12Mpa, cool to room temperature then.With the reaction product fragmentation, sieve, be that 3～5 stoichiometric sour 20L carry out pickling with equivalent concentration, be washed to the solution pH value again and be the oven dry of neutral back.To the dust sampling analysis of preparation, its chemical ingredients and weight percent and Fisher particle size see Table 1.
The chemical ingredients of table 1 ultra-fine high-nitrogen tantalum nitride powder of the present invention, weight percent be Fisher particle size when
As shown in table 1, the total nitrogen content of the ultra-fine high-nitrogen tantalum nitride powder that the inventive method is produced all is higher than 6.8% by weight percentage the time, be up to 7.39%, the total content of impurity F e, Ni, Cr, Si, K and Na etc. is less than 0.0090%, in the impurity level that allows usually, surplus is Ta, and powder Fisher particle size Fsss is all less than 1um (accompanying drawing 1 is the scanning electron microscope sem photo of embodiment 2, and all the other and this photo are basic identical).
Claims (2)
1. ultra-fine high-nitrogen tantalum nitride powder, it is characterized in that it is oxygen level≤0.4% with by weight percentage, the hypoxemia tantalum powder of Fisher particle size Fsss＜1 μ m is packed in the conventional vacuum reaction vessel, after being evacuated to pressure≤0.1Pa, be warmed up to 400～750 ℃, constant temperature charges into the high pure nitrogen of purity 〉=99.999% after 1 hour, be warmed up to 700～1200 ℃ again, and the maintenance nitrogen pressure is 0.02～0.16Mpa, constant temperature 3～5 hours, then behind the cool to room temperature with the reaction product fragmentation, sieve, remove impurity through pickling, be washed to again the pH value of solution value for neutrality after the nitrogen content by weight percentage that makes of oven dry be 6.8～7.40%, content of impurities＜0.0090%, surplus is the tantalum nitride powder of tantalum, the Fisher particle size Fsss of powder＜1 μ m.
2. ultra-fine high-nitrogen tantalum nitride powder, it is characterized in that it is oxygen level＞0.4% with by weight percentage, the hyperoxia tantalum powder of Fisher particle size Fsss＜1 μ m and consumption are that 2～10% magnesium powder thorough mixing of described hyperoxia tantalum grain weight amount is even, in the conventional vacuum of packing into the reaction vessel, after being evacuated to pressure≤0.1Pa, be warmed up to 400～550 ℃, constant temperature charges into the high-purity argon gas of purity 〉=99.999% after 1 hour, be warmed up to 700～800 ℃, constant temperature 2～5 hours, extract argon gas then, charge into the high pure nitrogen of purity 〉=99.999%, be warmed up to 950～1200 ℃ again, and the maintenance nitrogen pressure is 0.02～0.16Mpa, constant temperature 3～5 hours, then behind the cool to room temperature with the reaction product fragmentation, sieve, remove impurity through pickling, be washed to again the pH value of solution value for neutrality after the nitrogen content by weight percentage that makes of oven dry be 6.8～7.40%, content of impurities＜0.0090%, surplus are the tantalum nitride powder of tantalum, the Fisher particle size Fsss of powder＜1 μ m.
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| WO2015085476A1 (en) * | 2013-12-10 | 2015-06-18 | 宁夏东方钽业股份有限公司 | Method for preparing capacitor-grade tantalum powder with high nitrogen content, capacitor-grade tantalum powder prepared thereby, and anode and capacitor prepared from tantalum powder |
| WO2015100519A1 (en) * | 2013-12-30 | 2015-07-09 | 宁夏东方钽业股份有限公司 | Preparation method of high-nitrogen-content capacitor grade tantalum powder and tantalum powder prepared therefrom and tantalum capacitor |
| CN104071845B (en) * | 2014-07-15 | 2016-01-06 | 渤海大学 | A kind of SLTON perovskite typed oxynitride raw powder's production technology |
| CN104085926B (en) * | 2014-07-18 | 2016-05-11 | 渤海大学 | The preparation method of SLSTON Ca-Ti ore type nitrogen oxide solid-solution powder |
| CN104085927B (en) * | 2014-07-18 | 2016-03-09 | 渤海大学 | The preparation method of LSTON perovskite typed oxynitride solid-solution powder |
| CN107857240B (en) * | 2017-11-30 | 2021-03-30 | 株洲硬质合金集团有限公司 | Method for producing niobium nitride powder |
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Patent Citations (5)
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| JPS5514806A (en) * | 1978-07-13 | 1980-02-01 | Mitsubishi Metal Corp | Cubic boron nitride-containing sintered material for cutting tool |
| WO1994013419A1 (en) * | 1991-12-04 | 1994-06-23 | The Dow Chemical Company | A process for densifying powdered ceramics and cermets at temperatures above 1400 °c |
| JP2000264607A (en) * | 1999-03-12 | 2000-09-26 | Mitsui Mining & Smelting Co Ltd | Production of tantalum nitride |
| US6554884B1 (en) * | 2000-10-24 | 2003-04-29 | H.C. Starck, Inc. | Tantalum and tantalum nitride powder mixtures for electrolytic capacitors substrates |
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