CN102874775B - Preparation method of scandium nitride cubic crystal - Google Patents
Preparation method of scandium nitride cubic crystal Download PDFInfo
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- CN102874775B CN102874775B CN201210428159.4A CN201210428159A CN102874775B CN 102874775 B CN102874775 B CN 102874775B CN 201210428159 A CN201210428159 A CN 201210428159A CN 102874775 B CN102874775 B CN 102874775B
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Abstract
The invention provides a preparation method of scandium nitride cubic crystals, belonging to the technical field of preparation of a rare earth nitride nanometer material. The prepared scandium nitride cubic crystal comprises a regular cube or cuboid which has a flat and smooth surface and is uniform in appearance and dimension. With the adoption of the preparation method, the high-purity rare earth metal is directly reacted with nitrogen through a direct current arc plasma discharging device under the assistance of a high-temperature low-air pressure system condition and plasma, so as to prepare into powder with metallic luster and showing bluish green. According to the preparation method provided by the invention, the direct current arc plasma discharging device is utilized at the first time to synthesize scandium nitride cubic crystal which has high impurity and is uniform in appearance and dimension; the preparation method is simple, reliable, high in repeatability, short in reaction time, low in energy consumption, needs no the harsh vacuum condition, is environment-friendly, and has high output of products; and the scandium nitride cubic crystal has outstanding physical properties such as electricity, mechanics and the like, thus the scandium nitride cubic crystal can be widely applied in the fields of semiconductor devices and durable protecting coating and the like.
Description
Technical field
The invention belongs to the technical field of rare earth nitride nano material and preparation thereof, particularly a kind of method of preparing simply, efficiently scandium nitride cubic system.
Background technology
Transition metal nitride (Transition Metal Nitrides, TMN) because thering is high physical strength and the character of high rigidity, be widely used in for a long time the wear-resistant protecting layer of material, moreover, due to it, have the interesting physical attributes such as optics, electronics, magnetics simultaneously concurrently, make it in electronic industry field, have broad application prospects (Blackie Academic & Professional, London, 1996, pp.107 – 120.).Compare with traditional semiconductor material, transition metal nitride is that element N is inserted between the metalloid generating in transition metal lattice and fills type compound, and it is with the character of covalent compound, ionic crystal and 3 kinds of materials of transition metal.Due to the insertion of element N, cause metal lattice expansion, it is large that intermetallic distance and lattice constant become, interaction force between atoms metal weakens, the redistribution that produces corresponding d band contraction modification and near the density of states(DOS) of Fermi energy level, valence electron number increases, and structure also changes thereupon.The vacancy ratio in compound by tuning nitrogen and transition metal; electronic structure that can controlled material and transport attribute; this modulation makes transition metal nitride have number of chemical component; the change of component and electronic structure also makes this compounds have unique physics and chemistry performance; the application that these character are semiconducter device provides physical basis (Phys.Rev.Lett.86 (2001) 3348, Acta Mater.52 (2004) 173-180; J.Alloy.Compd.308 (2000) 178-188, J.Alloy.Compd.389 (2005) 42-46).
At present, due to the restriction of experimental technique means, the preparation work of ScN is rare progress still, and the work of minority mainly concentrates on preparation (Appl.Phys.Lett.77,2485 (2000) of thin-film material; J.Appl.Phys.84,6034 (1998); J.Appl.Phys.86,5524 (1999); J.Appl.Phys.90,1809 (2001)), and the condition of preparation is harsh, need high vacuum condition and very high temperature, preparation process is loaded down with trivial details, output is very low, and due to the limitation of thin-film material self application, has limited greatly to take the development of the semiconductor material that ScN is substrate.
The report that utilizes arc process to prepare ScN cubic crystal structure does not also occur.The most close with this patent be reported as (Journal of materials science:Materials in electronic 15 (2004) 555-559), in this report, utilize pure metal Sc distillation in advance in the atmosphere of nitrogen, prepare the former powder of ScN, and then the former powder of distillation ScN, on prepositioned tungsten paper tinsel, collect final ScN product.In contrast to this report, this patent utilizes pure metal Sc powder and the direct chemical combination of nitrogen, control experiment condition, one step is prepared the ScN Cubic Crystal Material of high purity, high yield, does not need loaded down with trivial details Repeated Sublimation-agglomeration process, without any need for deposition substrate, more do not need harsh vacuum condition, experimentation is simple and easy, simultaneously because electric arc self possesses the advantages such as product output is large, purity is high, experimental implementation is simple and easy, is beneficial to large-scale industrial production.
Summary of the invention
The technical problem to be solved in the present invention is to disclose a kind of ScN cubic system; Overcome the many restrictions in traditional preparation method, designed a kind of method of the ScN of preparation cubic system, the method is simple, reproducible, cost is low, catalyst-free, without template, without harsh vacuum condition, environmentally friendly, the output of the ScN cubic system of preparing is large, purity is high.
The present invention prepares the method for ScN cubic system, adopt the DC arc plasma electric discharge device of building voluntarily, details refers to patent: ZL 201110053887.7, detailed process is as follows: take high pure rare earth metals Sc, nitrogen is raw material, metal Sc(purity 99.99%) briquetting in advance, be pressed into diameter 12mm, the ingot metal of thickness 1 ~ 3mm.The metal Sc ingot suppressing is placed in graphite pot, put into the copper pot anode of direct current arc electric discharge device reaction chamber, tungsten bar negative electrode and copper pot anode are staggered relatively, first reaction chamber is evacuated to air pressure lower than 1Pa, be filled with high pure nitrogen (volume fraction is greater than 99.99%), repeat to be evacuated to lower than 1Pa to wash away air remaining in vacuum system, be then filled with high pure nitrogen and discharge to preset pressure 10 ~ 40kPa.During striking, setting flame current is 100 ~ 120A, and while keeping arc stability, voltage is 15 ~ 25V, and positive arc column section length is stable the stable of arc property curve that be beneficial to that 0.5 ~ 1cm(keeps arc column section length), the reaction of cutting off the electricity supply after the 5 ~ 15min that discharges approximately finishes.After reaction finishes, being filled with high-purity argon gas to internal pressure is 30 ~ 60kPa, the about 5h of passivation product.And after reaction finishes, keep recirculated water continuous flow commensurability 1h, object is in order to make reaction product keep original quench rates cooling gradually, and the product appearance and size obtaining is evenly distributed.After passivation completes, open vacuum chamber, in different temperature provinces, collect with metalluster, glaucous powder.
Technical scheme of the present invention can be summarized as described below.
A preparation method for scandium nitride cubic system, take rare earth metal scandium, nitrogen is raw material, in DC arc plasma electric discharge device, is prepared; Metal scandium powder is pressed into block, is placed in plumbago crucible, put into the copper pot anode of the reaction chamber of DC arc plasma electric discharge device, in copper pot anode, tungsten bar negative electrode and condenser wall, all pass into recirculated cooling water; Reaction chamber is evacuated to air pressure lower than 1Pa, and being filled with nitrogen to pressure is that 10 ~ 40kPa starts electric discharge; During striking, adjusting flame current is 100 ~ 120A, and while keeping arc stability, voltage is 15 ~ 25V, and positive arc column section length is 0.5 ~ 1cm, and the reaction of cutting off the electricity supply after the 5 ~ 15min that discharges finishes; Being filled with argon gas to internal pressure is 30 ~ 60kPa, passivation product 4 ~ 6h; And after finishing, reaction keep recirculated cooling water to continue circulation 1h; After passivation completes, open vacuum chamber, collect the powder with metalluster.
Described metal scandium, quality purity is not less than 99.99%; Described nitrogen, volume fraction is not less than 99.99%.
Described reaction chamber vacuumizes, and can before being filled with nitrogen, first reaction chamber be evacuated to air pressure lower than 1Pa, is filled with volume fraction and is 99.99% nitrogen, then be evacuated to lower than 1Pa, to wash away air remaining in reaction chamber (vacuum system).
The processing condition of the best of the present invention are, nitrogen pressure 20kPa, and electric current 100 ~ 120A, voltage 15 ~ 25V, positive arc column section length is 0.5cm, product is collected in 5min ， anodically deposit discharge time district.
In preparation process, in copper pot anode, tungsten bar negative electrode and condenser wall, all pass into water coolant; the object of stable temperature gradient field and condensation protection equipment not only can be provided in crystal growing process; while provides a quenching process fast after can and reacting in reaction process and finishing; be conducive to like this material nucleating growth in differing temps region, different quench rates, and then obtain the material of different-shape, size, structure.
According to method of the present invention, prepare scandium nitride cubic system product.
Scandium nitride cubic system product is that pattern is the lumphy structure of pseudo-cubic or rectangular parallelepiped by Sc, two kinds of elementary composition single crystal of N through characterizing, and cubic system is of a size of 20 ~ 50 μ m.
Beneficial effect of the present invention is, for ScN material, synthesizes first the ScN micrometer structure with pseudo-cubic or rectangular structure; ScN pattern corner angle are clearly demarcated, smooth surface is smooth, pattern homogeneous, degree of crystallinity are intact, be of a size of 20 ~ 50 μ m; Product output is large, purity is high, environmentally friendly; Reaction times is short, without catalysis, without template; Do not need harsh vacuum condition; Preparation method is simple, reproducible.
Accompanying drawing explanation
Fig. 1 direct current arc electric discharge device of the present invention structure iron.
Fig. 2 is the SEM figure of the ScN cubic system of collecting in anodically deposit district that makes of embodiment 2.
Fig. 3 is the EDX figure of the ScN cubic system of collecting in anodically deposit district that makes of embodiment 2.
Fig. 4 is the TEM figure of the ScN cubic system of collecting in anodically deposit district that makes of embodiment 2.
Fig. 5 is the selected area electron diffraction figure of the ScN cubic system of collecting in anodically deposit district that makes of embodiment 2.
Fig. 6 is the XRD spectra of the ScN cubic system of collecting in anodically deposit district that makes of embodiment 2.
Fig. 7 is the SEM figure of the ScN cubic system of collecting in negative electrode tungsten bar sedimentary province that makes of embodiment 2.
Fig. 8 is the SEM figure of the ScN cubic system of collecting in condenser wall sedimentary province that makes of embodiment 2.
Fig. 9 is the SEM figure of the ScN cubic system of collecting in anodically deposit district that makes of embodiment 3.
Figure 10 is the SEM figure of the ScN cubic system of collecting in anodically deposit district that makes of embodiment 4.
Embodiment
In conjunction with Fig. 1, illustrate and implement direct current electric arc device structure of the present invention.In Fig. 1,1 is the outer lens of direct current electric arc device, 2 is condenser wall, and 3 is tungsten bar negative electrode, and 4 is negative electrode tungsten bar sedimentary province, 5 is copper pot anode, 6 in copper pot for the graphite pot (it forms anode together with copper pot) of placing response initial feed, 7 is water outlet, 8 is water-in, 9 is inlet mouth, and 10 is air outlet.
In the present invention, can be in anodically deposit district (graphite pot region), 4(negative electrode 3 lower ends, negative electrode tungsten bar sedimentary province) and condenser wall sedimentary province (condenser wall 2) collect with metalluster, glaucous powder.
In copper pot anode 5, tungsten bar negative electrode 3 and condenser wall 2, all pass into water coolant for the key of preparation ScN cubic system, trizonal cooling circulating water system provides a stable temperature gradient field for whole discharge process, both the stability of high-temperature area arc column in tungsten bar negative electrode 3 and anode graphite pot in the time of can keeping discharging, can after stopping, electric discharge make again the temperature of anode graphite pot decline rapidly, reach the effect of quenching, finally obtain ScN cubic system.
The whole process of embodiment 2 preparation ScN cubic systems.
Take high pure rare earth metals Sc, nitrogen is raw material, metal Sc(purity 99.99%) briquetting in advance, be pressed into diameter 12mm, the ingot metal of thickness 1-3mm.The metal Sc ingot suppressing is placed in graphite pot, puts into the copper pot anode of the reaction chamber of direct current arc electric discharge device, tungsten bar negative electrode and copper pot anode are staggered relatively.First reaction chamber is evacuated to air pressure lower than 1Pa, is filled with high pure nitrogen (volume fraction is greater than 99.99%), repeat to be evacuated to lower than 1Pa to wash away air remaining in vacuum system, then pass into high pure nitrogen and discharge to preset pressure 20kPa.During striking, setting flame current is 100 ~ 120A, and while keeping arc stability, voltage is 15 ~ 25V, and positive arc column section length is stable the stable of arc property curve that be beneficial to that 0.5cm(keeps arc column section length), the reaction of cutting off the electricity supply after the about 5min that discharges finishes.After reaction finishes, being filled with high-purity argon gas to internal pressure is 30kPa, the about 5h of passivation product.Reaction finish to continue keeps the recirculated cooling water about 1h that circulates, and object is in order to make reaction product keep original quench rates cooling gradually, and the product appearance and size obtaining is evenly distributed.After completing, passivation opens vacuum chamber, what (graphite pot), negative electrode tungsten bar sedimentary province and condenser wall region were collected with metalluster in anodically deposit district respectively, glaucous powder.
Fig. 2 provides the SEM figure of the ScN cubic system of collecting in anode graphite pot, can find out that cubic system is of a size of 20 ~ 50 μ m, and corner angle are clearly demarcated, and smooth surface is smooth, and pattern is the lumphy structure of pseudo-cubic or rectangular parallelepiped.Fig. 3 provides the EDX figure of cubic system prepared by above-mentioned condition, can show that cubic system is only by Sc, and two kinds of N are elementary composition.Fig. 4 provides the TEM figure of ScN cubic system prepared by above-mentioned condition.Fig. 5, Fig. 6 provide selected area electron diffraction figure and the XRD spectra of cubic system prepared by above-mentioned condition, prove that ScN cubic system is monocrystalline, and crystal structure is good, and crystalline form is complete, and product purity is high.Fig. 7 is given in the scanning electron microscope picture of the ScN sample of collecting negative electrode tungsten bar sedimentary province, can find out, sample still keeps the pattern of cubic system, but size heterogeneity, there is crack in cubic system, surface imperfection increases.Fig. 8 provides the scanning electron microscope picture of the ScN sample of collecting in condenser wall region, can find out that sample cubic structure is destroyed, and plane of crystal dislocation defects increases, and cubic system crystalline form is deteriorated, out-of-shape and occur cavernous structure.
In the present embodiment, in anode graphite pot deposition region temperature, high and temperature field is stable, has optimum growing environment, easily forms the particle that degree of crystallinity is high, crystalline form is complete, and resulting ScN cubic system crystalline form is complete, size homogeneous.And negative electrode tungsten bar sedimentary province and condenser wall region be because decentering reaction zone is far away, thermograde is larger, and temperature field stability reduces, and reaction product is transported to sedimentary province by central section and has experienced very strong During Quenching, the degree of crystallinity of product and crystalline form variation.
The whole process of embodiment 3 preparation ScN cubic systems
The amount that changes reactant gases in embodiment 3 is 40kPa, and the reaction times is controlled at 15min, and all the other experiment conditions are identical with embodiment 2, and reaction finishes to collect in Hou anodically deposit district (graphite pot) metalluster, glaucous powder.Fig. 9 provides the scanning electron microscope picture of the resulting ScN sample of transformation of the way Preparation Method, and it is clearly demarcated that the prepared ScN cubic system of Image Display is similarly corner angle, and smooth surface is smooth, and pattern is the lumphy structure of pseudo-cubic or rectangular parallelepiped, is of a size of 20 ~ 50 μ m.
The whole process of embodiment 4 preparation ScN cubic systems
The amount that changes reactant gases in embodiment 4 is 10kPa, and the reaction times is controlled at 10min, and all the other experiment conditions are identical with embodiment 2, and metalluster, glaucous powder are still collected in reaction after finishing in anodically deposit district (graphite pot).Figure 10 provides the scanning electron microscope picture of the resulting ScN sample of this preparation method, and prepared sample big difference too not in the ScN cubic system that Image Display is prepared and embodiment 2,3 is still keeping the lumphy structure of accurate cube or rectangular parallelepiped.
In embodiment 3,4, change respectively gaseous tension and reaction times, in anode graphite pot sedimentary province, still collect metalluster, glaucous powder.Can think, reaction gas pressure and reaction times are little on the pattern of product and particle size impact.
Processing condition and the powder collecting zone of the preparation ScN cubic system of embodiment 5 the bests
Contrast above-described embodiment 2 ~ 4 is found the stability of reaction zone temperature fields, and the thermograde in reaction process, quench rates that different zones is different have obvious impact to the pattern of prepared product and size.Therefore as described in Example 2, the region that the generation of sample deposition is collected is anode graphite pot district ，Ji， anodically deposit district to the preparation condition of preferred preparation ScN cubic system.
In view of the feature that direct current arc self output is large, purity is high, simple to operate; the method of introducing in embodiment 2 is applicable to suitability for industrialized production very much, the physical attribute of ScN excellence for its in electronic industry field, the application in the field such as high-abrasive material, packaging protection material provides solid physical basis.
Claims (4)
1. a preparation method for scandium nitride cubic system, take rare earth metal scandium, nitrogen is raw material, in DC arc plasma electric discharge device, is prepared; Metal scandium powder is pressed into block, is placed in plumbago crucible, put into the copper pot anode of the reaction chamber of DC arc plasma electric discharge device, in copper pot anode, tungsten bar negative electrode and condenser wall, all pass into recirculated cooling water; Reaction chamber is evacuated to air pressure lower than 1Pa, and being filled with nitrogen to pressure is that 10～40kPa starts electric discharge; During striking, adjusting flame current is 100～120A, and while keeping arc stability, voltage is 15～25V, and positive arc column section length is 0.5～1cm, and the reaction of cutting off the electricity supply after the 5～15min that discharges finishes; Being filled with argon gas to internal pressure is 30～60kPa, passivation product 4～6h; And after finishing, reaction keep recirculated cooling water to continue circulation 1h; After passivation completes, open vacuum chamber, collect the powder with metalluster.
2. according to the preparation method of scandium nitride cubic system claimed in claim 1, it is characterized in that, described metal scandium, quality purity is not less than 99.99%; Described nitrogen, volume fraction is not less than 99.99%.
3. according to the preparation method of the scandium nitride cubic system described in claim 1 or 2, it is characterized in that, described reaction chamber vacuumizes, first reaction chamber to be evacuated to air pressure lower than 1Pa before being filled with nitrogen, be filled with volume fraction and be 99.99% nitrogen, be evacuated to again lower than 1Pa, to wash away air remaining in reaction chamber.
4. according to the preparation method of the scandium nitride cubic system described in claim 1 or 2, it is characterized in that, be filled with nitrogen pressure 20kPa, electric current 100～120A, voltage 15～25V, positive arc column section length is 0.5cm, product is collected in 5min ， anodically deposit discharge time district.
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| CN104692341A (en) * | 2015-02-17 | 2015-06-10 | 吉林大学 | SnSe square nanosheets and preparation method thereof |
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| CN104692341A (en) * | 2015-02-17 | 2015-06-10 | 吉林大学 | SnSe square nanosheets and preparation method thereof |
| CN104692341B (en) * | 2015-02-17 | 2016-06-22 | 吉林大学 | A kind of Tin monoselenide. square nanometer sheet and preparation method thereof |
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