CN1565966A - Non-crystal diamond material and manufacturing method and application thereof - Google Patents
Non-crystal diamond material and manufacturing method and application thereof Download PDFInfo
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- CN1565966A CN1565966A CN 03148262 CN03148262A CN1565966A CN 1565966 A CN1565966 A CN 1565966A CN 03148262 CN03148262 CN 03148262 CN 03148262 A CN03148262 A CN 03148262A CN 1565966 A CN1565966 A CN 1565966A
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Images
Abstract
The invention discloses a non-crystal diamond material and manufacturing method and application thereof adapted for the field of thermal emission and field emission, wherein the amount of electron ejection is maximized, the non-crystal diamond material contains at least 90% of carbon atoms, 30% of which are bonded through interlinkage of twisted tetrahedrons. The material has a plane of departure with an elevation of 10-10,000 nanometers.
Description
Technical field
The present invention mainly relates to non-crystal diamond material and manufacture method and application, particularly in a kind of device and manufacture method and application like generation electronics in the carbon material of diamond.Therefore, the application has comprised physics, chemistry, electronics and Materials science.
Background technology
A heat emission (Thermiomic Emission) and an emission (Field Emission) have many different utilizations already, for example cathode tube (Cathode Ray Tube), Field Emission Display (FieldEmission Display).
Usually heat emission refers to that electronics is heated and penetrates.Emission refers to that then electronics is ordered about by electric field and wears tunnel and penetrate.The example of these devices and description comprise following United States Patent (USP) 6,229,083; 6,204,595; 6,103,298; , 0064,137; 6,055,815; 6,039,471; 5,994,638; 5,984,752; 5,981,071; 5,874,039; 5,777,427; 5,722,242; 5,713,775; 5,712,488; 5,675,972; And 5,562,781 document etc.Though a lot of aspects that are applied in of electron emission all have quite successful example, the successful case of heat emission is than lacking that the field emission comes.Though an emission is easier to reach, be subject to shoot material, the restriction of disappearances such as elasticity, cost, life-span and efficient.
Many different materials be used in already field emission device in, and reach with less energy requirement, produce higher electric current output.Recently, a kind of material is arranged make industry produce suitable interest to it because of the characteristic of its physics, that is exactly a diamond.Particularly, diamond has a kind of approximate negatron avidity (NegativeElectron Affinity; NEA), the avidity of this negative value then can penetrate the electronics that adds easily.Yet diamond also has high energy gap (Band Gap), and also because like this, diamond also becomes a kind of electronics that prevents and passes through wherein, or the isolator that leaves.Once the someone was attempting going to improve or reduce the energy gap of diamond, for example was to add some impurity (Dopant) in diamond, or made diamond form the structure with geometry in particular.But these attempts still exist the restriction on effect, efficient and the cost therebetween.Therefore, in the application that the application of field emission device still is limited on the small scale and low current is exported.
Therefore, only need to draw quite a spot of energy and reach the material that high electric current is exported, still need seek this class material by the constantly effort of research and development by the power supply place.
Summary of the invention
The purpose of this invention is to provide a kind of non-crystal diamond material and manufacture method thereof and application, non-crystal diamond material combines the characteristic of material and geometry, the material of this class has comprised at least 90% carbon atom, and wherein at least 30% carbon atom is to be linked on the tetrahedron of distortion.The material of this class has still comprised an electron emission face, and it is to have by 10-10, the 000 rough height of rice how; On the other hand, the ratio that is linked at carbon atom on the tetrahedron of distortion is at least 50%, reaches behind the energy that obtains capacity the purpose of launching electronics in a vacuum.
The object of the present invention is achieved like this: a kind of non-crystal diamond material, it is characterized in that: it comprises at least 90% carbon atom, wherein at least 30% carbon atom be with the distortion the tetragonal body coordinate and bond together, this diamond material is to have the electron emission face, this electron emission mask has a concavo-convex roughness height, and this concavo-convex roughness height is 10-10,000 rice how, the energy of input capacity is to this diamond material, and this electron emission face is an emitting electrons.
This concavo-convex roughness height is 10,000 how below the rice.This concavo-convex roughness height is 100-1,000 rice how.This concavo-convex uneven surface is to have a peak density, this peak density be on emitting surface every square centimeter contain at least one 1,000,000 peaks.This concavo-convex uneven surface is to have a peak density, this peak density be on emitting surface every square centimeter contain at least ten hundred million peaks.
Having 50% carbon atom at least is that tetragonal body coordinate with this distortion combines.The energy of this input capacity be selected from following at least a: comprise heat energy, luminous energy, electric field energy or its combination.The temperature of this heat energy is less than 500 ℃.
The present invention also provides a kind of manufacture method of non-crystal diamond material, it is characterized in that: it comprises following step: a carbon source is provided; And utilize cathodic arc technique and form non-crystal diamond material.
The present invention provides a kind of application of non-crystal diamond material again, it is characterized in that: it is applicable to the device of emitting electrons, the device of this emitting electrons is to comprise non-crystal diamond material, electrode and anode, this non-crystal diamond material includes 90% carbon atom, wherein 30% be one the distortion the tetragonal body coordinate in combination, this diamond material is to have an electron emission face, and this electron emission face is to have a 10-10, the 000 concavo-convex roughness height of rice how; This electrode is to combine with this non-crystal diamond material and form a negative electrode; This anode is with the emitting surface of this non-crystal diamond material and mutual opposition, and between being across a vacuum space, this negative electrode adds the energy of a capacity, electronics enters this vacuum space from its emitting surface.
The device of this emitting electrons still has a gate, this gate be the position in this vacuum space, and be between this emitting surface and anode, this gate produces an electric field when adding a forward grid voltage.This gate is a wire netting.The device of this emitting electrons still has a low-energy positively charged ion in the vacuum space, this is low-yield to be to be enough to reduce to the interelectric repulsive force that is emitted from the electron emission face minimum.The low-energy positively charged ion of the device of this emitting electrons is to be selected from down at least a in the column element: it comprises lithium, sodium, potassium, rubidium, caesium, thulium, beryllium, magnesium, calcium, strontium, barium or its arbitrary combination.The low-energy positively charged ion of the device of this emitting electrons is a caesium.The concavo-convex roughness height of the emitting surface of the device of this emitting electrons is less than 10,000 rice how.The concavo-convex roughness height of the emitting surface of the device of this emitting electrons is 100-1,000 rice how.The concavo-convex uneven surface of the device of this emitting electrons is to have a peak density, this peak density be on emitting surface every square centimeter contain at least one 1,000,000 peaks.The peak density of the device of this emitting electrons be on emitting surface every square centimeter contain at least ten hundred million peaks.The carbon atom of the non-crystal diamond material of the device of this emitting electrons has at least 50% to be to be in the same place with the tetragonal body coordinate bond of distortion.The energy of the device of this emitting electrons be selected from following at least a: comprise heat energy, luminous energy, electric field energy or its combination.The temperature of the heat energy of the device of this emitting electrons is less than 500 ℃.The device of this emitting electrons is in order to as a motor.The device of this emitting electrons is in order to as a solar cell.The device of this emitting electrons is in order to as a refrigerating unit.This refrigerating unit is a radiating surface, and this radiating surface cools off a unicircuit.This refrigerating unit cools off a contiguous zone, and makes temperature be lower than 100 ℃.This electrode is coated with this non-crystal diamond material, in order to strengthen the electronics output of this electrode.To this electrode coating non-crystal diamond material, in order to the working life of this electrode that extends.This electrode is the some of battery.This electrode is the some of electric deposition device.This electrode is the some of luminous source device.
The rough height of the emitting surface of the device of emitting electrons of the present invention also can have many different structures, and rough height of the present invention is to be approximately 10,000 how below the rice, is preferably to be approximately 1,000 rice how.
Except the height parameter, this rough emitting surface also has some density peaks parameter, the density peaks that this rough emitting surface had at least every square centimeter contain 1,000,000 peak values.Preferable density peaks at least every square centimeter contain 100,000,000 peak values.
The many different form of energy that merges of heat energy, photon energy, electric field energy or above-mentioned each energy for example, can be changed by material of the present invention, and can quicken the stream of electrons that penetrates by this material, the form of this energy then may be by itself employed heat energy, or and the merging of electric field energy.On the other hand, this energy may be itself employed photon energy (luminous energy just), or and the energy that merges of electric field energy.The another kind of possible energy then is electric field energy.Many different energy intensities can use according to need, are using the required electric current of generation under the material of the present invention.The intensity of this energy can be made decision partly by the form of the employed certain material of reality, rough emitting surface and the intake that uses.This energy may be the heat energy that has less than 500 ℃ of temperature.
Non-crystal diamond material of the present invention also can combine with many different peripheral componentss or unite, so that on many devices of making a profit in can characteristic by material itself, and emitting electrons in vacuum.For example, form a device of emitting electrons this reciprocatable joining together of so-called non-crystal diamond material, this device then still has one and non-crystal diamond material and is coupled together mutually, to form a negative electrode and anodic electrode, wherein, anode is the face of accepting with respect to non-crystal diamond material, and is and the emission of cathode face vacuum space that is separated by, if after negative electrode has been imported enough energy, then can launch electronics at vacuum chamber.
Other different element also can be under needs and is added, and finishes a specific device.Electron emitting device still can comprise a gate, and it is to be positioned at the vacuum space, and accepts between the face at emission of cathode face and anode, and when supply one voltage gave this gate, this gate can produce an electric field.This gate can be a metal screen.On the other hand, this vacuum space also can add a certain low-energy positively charged ion, and these positively charged ions can reduce to the interelectric repulsive force that is emitted by the electron emission face minimum completely.Being fit to cationic example is to include but not limited to lithium, sodium, potassium, rubidium, caesium, thulium, beryllium, magnesium, calcium, strontium, barium, or the mixing of above-mentioned each element.Preferable this positively charged ion can be a caesium.
Every ripe in this skill person, can recognize that non-crystal diamond material can be used on many different devices, and be used for different purposes.The scope of this type of device also has other various device including but not limited to large size or undersized motor, refrigerating unit, transistor, switch, expander, negative electrode, electrode and annular laser gyrostat.This device can be a motor; An or refrigerating unit.This refrigerating unit can be reduced to the temperature of an adjacent domain and be lower than about 100 ℃.
Non-crystal diamond material of the present invention can use the known different technologies of industry to make.And the carbon source that need provide has been be provided this type of method, and desire forms the employed deposition method of non-crystal diamond.
Method of the present invention is by using a kind of cathodic arc technique to form non-crystal diamond material.
The prior characteristic of the present invention is summarized out, is not to show in the mode that enlarges, and so, detailed description after this can be easier to allow the people understand, and contribution of the present invention also can be made us knowing from experience.
Describe in detail below in conjunction with preferred embodiment and accompanying drawing.
Description of drawings
Fig. 1 is the schematic side view of non-crystal diamond material of the present invention;
Fig. 2 is the schematic side view of the non-crystal diamond material of Fig. 1, and it is to become one after absorbing enough energy, the device of emitting electrons in vacuum with different unit construction;
Fig. 3 is the schematic perspective view of diamond material of the present invention, and it is made by the cathode arc program;
Fig. 4 is the part enlarged diagram of non-crystal diamond material shown in Figure 3;
Fig. 5 is of the present invention by the map of current that electric field produced that non-crystal diamond material brought out;
Fig. 6 is the diamond tetrahedron with tetrahedron coordinate of general or normal carbon bond knot of the present invention;
Fig. 7 is the non-general or diamond tetrahedron of the tetrahedron coordinate of disordered carbon bond that has of the present invention.
Embodiment
Before the present invention begins to disclose or illustrates, must recognize, the present invention is subject to these specific structures, step or disclosed material, but can extend to other similar structure, step or material, this is like being for ripe for this skill person in the relevant industries, is can utilize the revealer of institute and in addition the overline combination is general.Also need recognize that at this employed example only be to be used to illustrate particular specific embodiment, rather than be to limit the present invention.
What must notice is: in specification sheets and protection domain, a of odd number, an and the have most reference values, only in the literary composition clear and definite explanation its be meaning with other.Therefore, " diamond grains " comprised one or more diamond grains, and " carbon source " then is to have comprised one or more carbon source, and one " cathodic arc technique " then comprised one or more this type of technology.
Describing and advocating that when of the present invention, employed term will be used according to following definition:
1, " vacuum " used in the present invention refers in the situation of pressure condition less than the 10-2 Bristol.
2, " diamond " used in the present invention refer to carbon atom and other carbon atom with a kind of network mode of well-known sp3 bond bond a kind of structure together.Particularly, each carbon atom is to be surrounded by four carbon atom, and with its bond mutually, each carbon atom also is the top of being located in positive tetrahedron.In addition, the bond length between two carbon atoms is 1.54 dusts (), and the angle between any two bonds is 109 degree 28 minutes and 16 seconds under the normal temperature state.Normal tetrahedral structure is shown in Fig. 6 between carbon atom.The structure of diamond and character comprise its physical property and electrically then are that industry is known.
3, " the tetrahedron coordinate of distortion " used in the present invention tetrahedral bonds junction structure of referring to carbon atom is irregular, has produced distortion by the structure of above-mentioned normal diamond positive tetrahedron.The distortion of this kind normally because of or some bond long in the length of some bond too short due to, simultaneously, between the angle of bond, produce variation and also can cause same result.In addition, tetrahedral distortion has changed the feature and the characteristic of carbon, makes its sp between between carbon atom
3Bond structure (diamond just), or sp
2Between the bond structure (graphite just).One contain carbon atom with the distortion tetragonal body and the example of bond material together is exactly a non-crystal diamond.Carbon atom then is presented at Fig. 7 with the tetragonal body coordinate bond representative graph together of distortion.
4, " non-crystal diamond " used in the present invention refers to a kind of material, and it is to be main element with carbon atom, and it is a large amount of carbon atom bond is together with the tetragonal body coordinate of distortion with the carbon atom of distortion.It should be noted that: many different elements can also be impure or the mode of impurity and being present in the carbonaceous material, and these elements are then including but not limited to hydrogen, sulphur, phosphorus, boron, nitrogen, silicon, tungsten etc.The content of carbon can be at least 90% in non-crystal diamond material, wherein then at least 30% carbon be with the distortion the tetragonal body bond together.
5, " coarse " used in the present invention refers to by when doing surface analysis, the assessment of doing for the different characteristic of the concavity and convexity on surface.Many diverse ways all can be used as the pointer of surfaceness, for example peak or the height of protrusion from the teeth outwards, or in the surperficial trench or the degree of depth of depression.In addition, measure concavo-convex method and comprised peak or the quantity of depression (the just peak or the density of depression) in a specific zone, and the distance between between peak or depression.
What 6, " containing metal " used in the present invention referred to is exactly a kind of metal, or a kind ofly contains two kinds or the alloy of multiple metal.For this skill person, it is to know many different metallic substance for ripe, and for example aluminium, copper, chromium, iron, steel, stainless steel, titanium, tungsten, zinc, zirconium, molybdenum etc. have also comprised the alloy and the synthetics of above-mentioned metal simultaneously.
7, " substantial " used in the present invention when the number of material or quantity, or during a certain characteristic of this material, it refers to: it is enough to provide the amount of the effect that this material or characteristic expection can provide.
8, " not having in fact " used in the present invention noun is used for a kind of number or when amount of material, or during a certain characteristic of this material, it refers to: lack this material or this characteristic, or the amount of this material or characteristic is to be enough to teach a measurable effect, and this measurable effect is normally taught by this kind material or characteristic.
9, " electron affinity " used in the present invention refers to: an atom attracts in the one track or in conjunction with the trend of an electronics.
10, " negatron avidity " used in the present invention (NEA) refers to the trend of atom refusal unbound electron, or under the energy input of an a small amount of, can discharge the trend of electronics in its track.Those are ripe in this skill person, when recognizing that negatron avidity is composition or its geometry that can be by material or the comprehensive method of aforesaid way forms.
11, the data on concentration, quantity and other numerical value is that form with a kind of scope is presented or represents.The use that should recognize this kind range format only is based on accessibility and succinct, therefore when explaining, should have its elasticity and can comprise except citation clear and definite in scope coming out and as other numerical value the numerical value of restriction, also can be included in simultaneously interior all individual number of numerical range or underrange that institute quotes from out, this just looks like to be that each numerical value and underrange are that clear and definite quilt is quoted from out.
12, as example, a numerical range " about one micron to about five microns " should be construed to and not only comprise about one micron to about five microns that clearly citation is come out, and also should be included in each numerical value and underrange in this specified scope simultaneously.Therefore, be contained in each numerical value in this numerical range, for example 2,3 and 4, or the underrange of 1-3,2-4 and 3-5 etc. for example.This principle also is applicable to only quotes from a single numerical value.No matter the institute's description scope or the width of characteristic are answered in this explanation, and are applicable to any situation without exception.
The invention relates to a kind of non-crystal diamond material and manufacture method thereof and application, it is behind input one enough energy and produce electronics under vacuum.
As in background technology, using many different materials all is to be that attempt reaches this purpose, and it is to have comprised diamond material and disclosed device in WO 01/39235.Because the characteristic of its high energy gap, the crystallization diamond also is not suitable for being used as an electronic emitter, unless its revised, to reduce or to change its energy gap.Therefore, be used to change the technology of diamond band gap, for example diamond soaked and moisten in different admixtures, and revise diamond structures,, all make the use generation of electronic emitter make us querying so that it has some structural feature etc.
Many different non-crystal diamond materials can be in supply emitting electrons during one energy source and easily.These materials are the NEA characteristics with diamond, but can't be subjected to the puzzlement of the band gap issues of pure diamond.So electrons excited is to pass through non-crystal diamond material like a cork by institute's supplying energy, and use less diamond to use energy still less to be launched.
Non-crystal diamond material of the present invention is the absorption region with a kind of high energy, and can allow broader energy be converted into electronics, promotes the efficient of conversion.
Many differences, and the specific non-crystal diamond material of required feature can be provided is to be included within the present invention.But the non-crystal diamond of relevant accelerated electron emission of the present invention promptly is the tetragonal body coordinate of its distortion, and the tetragonal body coordinate by this distortion, the in addition combination of many carbon atoms.
The tetragonal body coordinate can allow carbon atom obtain sp
3The bond characteristic, this then can promote the surface appearance that NEA is required.Simultaneously, because the bond of the different lengths of carbon atom, it also can provide most different and effective energy gaps of planting.Based on this, the problem of the energy gap of pure diamond has just overcome, and non-crystal diamond material can be in emitting electrons under the vacuum.
Can comprise about at least 90% carbon atom at non-crystal diamond material of the present invention, and comprise at least then that wherein 30% carbon atom is that bond is together with the tetragonal body coordinate of distortion.
Can comprise that at non-crystal diamond of the present invention at least 50% carbon atom is that bond is together with the tetragonal body coordinate of distortion.
Consult shown in Figure 1ly, can promote that relevant for non-crystal diamond of the present invention electron emission is its structure of how much.A specific embodiment of the structure of the non-crystal diamond of making according to the present invention 5.Particularly, non-crystal diamond material is to have one can accept energy, for example is the energy input face 10 of heat energy, and one can be by this place the electron emission face 15 of emitting electrons.In order more to promote the emission of electronics, this electron emission face 15 is to have a uneven or emitting surface of roughness, and it is can concentrate stream of electrons and add strong current output, is by most peaks and protrudes 20 and form in the roughness that this presented.
When many conventional apparatus all once attempted to concentrate electronics, for example, concentrate electronics by teaching most mound shapes or taper to an emitting surface, wherein without any a device under the situation of using an energy input, and reach the demand that high electric current with multiple different application is exported.In addition, this kind shortcoming is owing to mound shape, taper etc. are all too big, so that its density is also too little, thus can't concentrate electronics according to demand, and strengthen stream of electrons.The size of traditional method in height is greater than most microns usually, and therefore allowing less than every square centimeter only is 1,000,000 protrusion density.But when nano carbon tubes can reach than the higher output of other traditional projector, nano carbon tubes had shown its vulnerability, short life cycle simultaneously, and the defective that does not also match on electrical level and stream of electrons.
The roughness of emitting surface of the present invention is to have by 10 to 10,000 height of rice how.The height of this roughness may be to have about 10,000 rice how, or has about 1,000 rice how.In addition, roughness can be to have peak density to be at least on emitting surface, every square centimeter of nearly 1,000,000 peaks, or roughness can be to have peak density to be at least on emitting surface, every square centimeter of nearly 100,000,000 peaks, or roughness can be to have peak density to be at least on emitting surface, every square centimeter of nearly 1,000,000,000 peaks.The height of any numeral and the combination of density all can be used, and to reach a kind of specific emitting surface roughness, this roughness then is to be used for producing electronics to export required.Roughness is to comprise being 10 approximately at least, 000 height of rice how, or on emitting surface greater than the about density at 1,000,000 peaks of every square of metric cube, roughness is to comprise being 1 approximately at least, 000 height of rice how, or on emitting surface greater than the about density at 1,000,000,000 peaks of every square of metric cube.
Non-crystal diamond material of the present invention is to utilize many different energy input patterns to produce electronics.Then comprise about the example of suitable energy but be not to be limited to, high temperature or heat energy, light or luminous energy and electric field energy.All ripe in this skill person, when recognizing that other is suitable for so that the electron production in non-crystal diamond material is effectively shaken, so that the release of material and the energy pattern of passing through and leaving also can be used.In addition, the combination of different-energy also can be used, and reaching a specific result, or the function that equity decide device modified, so as non-crystal diamond can and its cooperation.
Energy pattern used in the present invention can be a heat energy.A kind of energy absorber then can produce related with non-crystal diamond of the present invention or be coupled together mutually, so then can assist to the absorption of heat and with thermal conversion to material.Knowing this skill person, can to realize this kind resorber be to have comprised many storing in advance can absorb the material of heat energy, for example black carbon etc.Can have by the heat energy that non-crystal diamond material absorbed and to be lower than 500 ℃ temperature.
The present invention can be electric field energy (a grid bias-voltage just) in order to the energy that promotes stream of electrons.This electric field energy utilize following gate or utilize those for ripe be to be applied to non-crystal diamond material in this skill person for the mechanism of quite haveing the knack of.
Non-crystal diamond material of the present invention can also be worked in coordination with or combination mutually with many different elements, can produce different devices.
Consult shown in Figure 2ly, it is the made motor of the present invention.It should be noted that: non-crystal diamond material 5 is to have an electrode 25 that is coupled together mutually with energy input face 10, and forms a negative electrode.In addition, a kind of energy harvester 40 is with this electrode 25 and coupling mutually.Energy harvester 40 can be included within the present invention according to need, strengthens the heat energy or the collection of luminous energy and is transmitted into non-crystal diamond material.An anode 30 is the emitting surface 15 that are close to non-crystal diamond material, then is by a vacuum space 35 emitting surface 15 and anode to be separated therebetween.The gate 45 that can comprise an electric field is to be placed within the vacuum space 35, and is close to emitting surface 15, and in one aspect, then is to come coupling with it, or can be connected with it, for example is by a kind of dielectric support (not shown).Those are ripe can or should to be added in the assembly shown in Figure 2 when the element that can understand other easily in this skill person, reaching a certain specific target, or makes a device especially.Do not lie under the situation of restriction, a wire 50 is can be placed between negative electrode and the anode, and finishes a whole circuit, allows electric current pass through, and allows the one or more device (not shown)s of electric current that need operate, or exercises other work.
In addition, the input and output line, for example be that a power supply (not shown) can be connected with this gate, and provide needed electric current, bring out an electric field, or the postivie grid bias-voltage, general like the element that is other needs, reach a specific device, this for ripe be can understand quite easily in this skill person.
Above-mentioned element can have different structures, also may be made by different materials.Gate 45 can be to be made by a conduction or metallic substance, can also be coupled together mutually by an isolator (not shown) simultaneously with emitting surface 15, and this isolator then to can be used as be a spacer or support.Gate can be a metal screen or a screen cloth.This kind screen or screen cloth can be supported at the side that installs, and only come to separate with emitting surface by this vacuum space.When structure is that aforesaid needs for isolator have just no longer included this demand as this moment.In addition, for the electro-conductive material that is fit to of electrode 25 and anode 30 for those ripe for this skill person be quite easily full of beard and.This type of material and structure partly are to be decided by the function of installing, and this device then this assembly merges.
Hindering or at least in a certain degree is slowed down most reasons by the emitting surface emitting electrons, one is the electronics that is transmitted into already in the space, true chamber.Particularly, the Electronic Negative electric charge that appears in the vacuum space repels the electronics that can be transmitted in the vacuum space in one aspect.So, this vacuum space is the low energy positively charged ion that can comprise an amount, and it is to be enough to and will to reduce to minimum between interelectric repulsive force.Most positively charged ions of planting are quite to be suitable for this purpose, and it is to comprise but be not to be limited to lithium, sodium, potassium, rubidium, caesium, thulium, beryllium, magnesium, calcium, strontium, barium etc., with and composition thereof, positively charged ion is preferable can be the strontium positively charged ion.
Because electronics is can utilize non-crystal diamond material of the present invention and the event of generation easily, has comprised that the stream of electrons that uses an electric field can quicken the absorption of heat energy at the electronics input side, can allow electronic emitter of the present invention become a refrigerating unit.Therefore, present invention includes a kind of refrigerating unit, it is can be by electron emission is absorbed heat energy to vacuum in the electric field that brings out.The element that this class device can have different forms and use many supports, it is like being above-mentioned motor.Refrigerating unit can be cooled near zone and be lower than 100 ℃.
Employed in the present invention non-crystal diamond material can via use ripe in this skill person institute detail knowledge many diverse ways and produce.This material or can be via using a kind of cathode arc mode obtain.The method of many cathode arcs is quite known for this skill person for ripe, for example in United States Patent (USP) the 4th, 448,799; 4,511,593; 4,556,471; 4,620,913; 4,622,452; 5,294,322; Disclose in 5,458,754 and 6,139964, generally speaking, cathodic arc technique has included carbon atom at a subject matter or the evaporation deposition of suprabasil physics (Physical Vapor Deposition; PVD).Electric arc is by a big electric current is passed a Graphite Electrodes that is used as negative electrode, and carbon atom is vaporized with this electric current.The carbon atom of vaporization also gives ionization simultaneously, with the portability positive charge.The negative-grid bias-voltage of varying strength is to be used for driving carbon atom towards a conduction target.If carbon atom has the energy (just about 100eV) of capacity, it will clash into target compound, and adheres in its surface, to form a material containing carbon, for example non-crystal diamond.
Generally speaking, how much contained energy is to obtain by the amount of adjusting the grid bias-voltage in atom, and deposition then can be controlled by the control flame current.Also can adjust simultaneously the twisting coefficient (sp just of carbon atom tetragonal body coordinate for these parameters and other parameter control
3/ sp
2And how much or the structure of non-crystal diamond material (also just for example is that a kind of high negative-grid bias-voltage is can quicken carbon atom and increase sp ratio),
3Bond).
In addition, increase flame current and can increase the impact rate of high-throughout carbon ion target.Therefore, under the situation that temperature raises, sedimentary carbon will be converted into more stable graphite.So the final structure of non-crystal diamond material and composition (just its energy gap, NEA and emitting surface roughness) all can be controlled by the situation of controlling the cathode arc that forms at this material.
Non-crystal diamond material of the present invention also can be applicable to have the condition shape of barometric point or positive pressure.For example, electrode and negative electrode can be designed so that to use non-crystal diamond material, for example coating layer of metal electron emission material on fluorescent tube bulb.In this case, not only the function of non-crystal diamond coating is the usefulness as protection, has also extended widely the working life of metal electrode simultaneously, and also can assist the emission of electronics.Therefore, requiredly can reduce greatly, and it also can reduce the temperature of metal electron emitter in order to the gas in the bulb is given luminous voltage.This combination with various advantages can extend the working life of luminescent lamp synergistically significantly.
In addition, other need also can obtain similar advantage by the device that emitting electrons produces light, and for example scanner, duplicating machine, lcd screen then are that the light of automobile is that other also has various application in addition.
In addition, non-crystal diamond also can be coated on general electrode, with flowing of accelerated electron.The electrode of this class can be applied in the galvanic deposit of battery and metal, for example electroplates.This type of electrode is can be used in the solution of water.For example, in order to monitoring water quality by measuring resistivity of water, or the electrode of edible things such as fruit juice, beer, soda for example.Because etch-proof characteristic, the electrode of non-crystal diamond have produced great advantage for traditional electrode.
Amorphous diamond electrodes has tangible advantage especially in some specific application, that is exactly an electro-deposition applications.Particularly, most of electric deposition devices the problem that can suffer from be exactly because electrode has absorbed the different polarization that gas produced.Yet,, be can't polar the most at last by the made electrode of non-crystal diamond based on the intensive inertia speciality of non-crystal diamond.
In addition, the inert speciality has also formed the normal high electrical potential energy that is in the aqueous solution.Under normal situation, this voltage will evaporate water.Based on the high electrical potential energy of having of non-crystal diamond, the solute in solution will be separated out before the water evaporation.This specific character will be suitable useful, and it can utilize the electrical potential energy of high oxidation that element is given galvanic deposit, and for example lithium and sodium though be suitable difficulty, are basic impossibilities in the past.
One similar aspect because the noble potential energy of being reached in solution by non-crystal diamond, the solute that presents with atomic a small amount of can be by separating out in the solution, and detect out.Therefore, material of the present invention is in that to make tool high responsive and can measure in solution, and it is suitable useful for example having on the diagnostic tool that is lower than the plumbous different elements of part per billion (ppb) or the device.This application has comprised any element that can separate out or be adsorbed on the electric charge, and it has comprised biochemical material, for example is the body fluid of blood and other urine etc.
Based on above-mentioned explanation, present invention includes in the manufacture method of this illustrated diamond material and the method for use.Except above-mentioned motor of mentioning and refrigerating unit, but the device of a lot of and work theoretical based on emitting electrons in a vacuum also the application of the invention non-crystal diamond material and benefit a great deal.Many can be by knowing the device that this skill person can realize, comprised but be not limited to transistor, supper-fast switch, annular laser gyrostat, current amplifier, microwave emitter and other electron beam device.
A kind ofly the method that enough energy come the manufacturing non-crystal diamond material of emitting electrons be can absorb in a vacuum, the step that a carbon source is provided, the method that forms the step of non-crystal diamond material and use a kind of cathode arc by the carbon source of being prepared comprised.This kind method also can comprise on emitting surface collaborative or coupling in a gate, can when an electric field is provided, strengthening the emission of electronics.In addition, present method has also comprised can positively charged ion at the end of emitting surface placed around under vacuum, its amount how much be to be enough to reduce to the interelectric repulsive force that is emitted by the electron emission face minimum.
A kind of stream of electrons or method of electric current of producing in a vacuum comprised the step of formation non-crystal diamond material described herein, and imports the energy that is enough to produce stream of electrons in this material.
It what follows is the example that is to illustrate according to the whole bag of tricks of manufacturing electronic emitter of the present invention.
Consult Fig. 3-shown in Figure 5, a kind of non-crystal diamond material is to use cathodic arc deposition and makes.Camber that it should be noted that emitting surface is to have about 200 height of rice how, and to have every square centimeter approximately be the peak density that 1,000,000 peaks are arranged.In making this kind material, at first, a kind of silica-based N type wafer with (200) orientation is to come etching about 20 minutes by mercury ion.Secondly, etched Silicon Wafer then is to utilize by Multi-Arc Rodkaway, and the Tetrabond of Niu Zexi manufacturing is coated with.The Graphite Electrodes of coating system is vaporized and forms the electric arc with 80 amperes, and this electric arc then can be by the negative-grid bias-voltage of one 20 volts of voltages guiding silicon substrate, and in this silicon substrate place deposition.Remaining non-crystal diamond material then is by removing in this coating system, and observes under an atomic force microscope, as shown in Figure 3 and Figure 4.
Consult shown in Figure 5, non-crystal diamond material thereafter then with electrode coupling mutually, forming a negative electrode, and provide a grid bias-voltage that adds.By the electric current that non-crystal diamond material produced then is as measurement and record in addition as shown in Fig. 5.
Certainly, should recognize that above-mentioned explanation only is the application that is to describe theory of the present invention.The modification of countless versions and become can development be come out not breaking away under spirit of the present invention and the category in this skill person by ripe, the therefore spirit according to the present invention modification and the change of doing all belongs within protection scope of the present invention.
Though the present invention is by specific example and is regarded as the most practical most preferred embodiment and is described in detail; for knowing this skill person; modify including but not limited to the change in described size, material, shape, form, function and operational method, assembly and the use, all contain and be placed among the protection of the present invention.
Claims (37)
1, a kind of non-crystal diamond material, it is characterized in that: it comprises at least 90% carbon atom, wherein at least 30% carbon atom be with the distortion the tetragonal body coordinate and bond together, this diamond material is to have the electron emission face, this electron emission mask has a concavo-convex roughness height, and this concavo-convex roughness height is 10-10,000 rice how, the energy of input capacity is to this diamond material, and this electron emission face is an emitting electrons.
2, non-crystal diamond material according to claim 1 is characterized in that: this concavo-convex roughness height is 10,000 how below the rice.
3, non-crystal diamond material according to claim 1 is characterized in that: this concavo-convex roughness height is 100-1,000 rice how.
4, non-crystal diamond material according to claim 2 is characterized in that: this concavo-convex uneven surface is to have a peak density, this peak density be on emitting surface every square centimeter contain at least one 1,000,000 peaks.
5, non-crystal diamond material according to claim 3 is characterized in that: this concavo-convex uneven surface is to have a peak density, this peak density be on emitting surface every square centimeter contain at least ten hundred million peaks.
6, non-crystal diamond material according to claim 1 is characterized in that: having 50% carbon atom at least is that tetragonal body coordinate with this distortion combines.
7, non-crystal diamond material according to claim 1 is characterized in that: the energy of this input capacity be selected from following at least a: comprise heat energy, luminous energy, electric field energy or its combination.
8, non-crystal diamond material according to claim 7 is characterized in that: the energy of this input capacity is a heat energy.
9, non-crystal diamond material according to claim 7 is characterized in that: the energy of this input capacity is a luminous energy.
10, non-crystal diamond material according to claim 7 is characterized in that: the temperature of this heat energy is less than 500 ℃.
11, a kind of manufacture method of non-crystal diamond material is characterized in that: it comprises following step: a carbon source is provided; And utilize cathodic arc technique and form non-crystal diamond material.
12, a kind of application of non-crystal diamond material, it is characterized in that: it is applicable to the device of emitting electrons, the device of this emitting electrons is to comprise non-crystal diamond material, electrode and anode, this non-crystal diamond material includes 90% carbon atom, wherein 30% be one the distortion the tetragonal body coordinate in combination, this diamond material is to have an electron emission face, and this electron emission face is to have a 10-10, the 000 concavo-convex roughness height of rice how; This electrode is to combine with this non-crystal diamond material and form a negative electrode; This anode is with the emitting surface of this non-crystal diamond material and mutual opposition, and between being across a vacuum space, this negative electrode adds the energy of a capacity, electronics enters this vacuum space from its emitting surface.
13, the application of non-crystal diamond material according to claim 12, it is characterized in that: the device of this emitting electrons still has a gate, this gate be the position in this vacuum space, and be between this emitting surface and anode, this gate produces an electric field when adding a forward grid voltage.
14, the application of non-crystal diamond material according to claim 13 is characterized in that: this gate is a wire netting.
15, the application of non-crystal diamond material according to claim 12, it is characterized in that: the device of this emitting electrons, still have a low-energy positively charged ion in the vacuum space, this is low-yield to be to be enough to reduce to the interelectric repulsive force that is emitted from the electron emission face minimum.
16, the application of non-crystal diamond material according to claim 15 is characterized in that: the low-energy positively charged ion of the device of this emitting electrons is to be selected from down at least a in the column element: it comprises lithium, sodium, potassium, rubidium, caesium, thulium, beryllium, magnesium, calcium, strontium, barium or its arbitrary combination.
17, the application of non-crystal diamond material according to claim 16 is characterized in that: the low-energy positively charged ion of the device of this emitting electrons is a caesium.
18, the application of non-crystal diamond material according to claim 12 is characterized in that: the concavo-convex roughness height of the emitting surface of the device of this emitting electrons is less than 10,000 rice how.
19, the application of non-crystal diamond material according to claim 18 is characterized in that: the concavo-convex roughness height of the emitting surface of the device of this emitting electrons is 100-1,000 rice how.
20, the application of non-crystal diamond material according to claim 18 is characterized in that: the concavo-convex uneven surface of the device of this emitting electrons is to have a peak density, this peak density be on emitting surface every square centimeter contain at least one 1,000,000 peaks.
21, the application of non-crystal diamond material according to claim 20 is characterized in that: the peak density of the device of this emitting electrons be on emitting surface every square centimeter contain at least ten hundred million peaks.
22, the application of non-crystal diamond material according to claim 12 is characterized in that: the carbon atom of the non-crystal diamond material of the device of this emitting electrons has at least 50% to be to be in the same place with the tetragonal body coordinate bond of distortion.
23, the application of non-crystal diamond material according to claim 12 is characterized in that: the energy of the device of this emitting electrons be selected from following at least a: comprise heat energy, luminous energy, electric field energy or its combination.
24, the application of non-crystal diamond material according to claim 23 is characterized in that: the energy of the device of this emitting electrons is a heat energy.
25, the application of non-crystal diamond material according to claim 23 is characterized in that: the energy of the device of this emitting electrons is a luminous energy.
26, the application of non-crystal diamond material according to claim 24 is characterized in that: the temperature of the heat energy of the device of this emitting electrons is less than 500 ℃.
27, the application of non-crystal diamond material according to claim 23 is characterized in that: the energy of the device of this emitting electrons is an electric field energy.
28, the application of non-crystal diamond material according to claim 12 is characterized in that: the device of this emitting electrons is in order to as a motor.
29, the application of non-crystal diamond material according to claim 12 is characterized in that: the device of this emitting electrons is in order to as a solar cell.
30, the application of non-crystal diamond material according to claim 12 is characterized in that: the device of this emitting electrons is in order to as a refrigerating unit.
31, the application of non-crystal diamond material according to claim 30 is characterized in that: this refrigerating unit is a radiating surface, and this radiating surface cools off a unicircuit.
32, the application of non-crystal diamond material according to claim 30 is characterized in that: this refrigerating unit cools off a contiguous zone, and makes temperature be lower than 100 ℃.
33, the application of non-crystal diamond material according to claim 12 is characterized in that: this electrode is coated with this non-crystal diamond material, in order to strengthen the electronics output of this electrode.
34, the application of non-crystal diamond material according to claim 12 is characterized in that: to this electrode coating non-crystal diamond material, in order to the working life of this electrode that extends.
35, according to the application of claim 33 or 34 described non-crystal diamond materials, it is characterized in that: this electrode is the some of battery.
36, according to the application of claim 33 or 34 described non-crystal diamond materials, it is characterized in that: this electrode is the some of electric deposition device.
37, according to the application of claim 33 or 34 described non-crystal diamond materials, it is characterized in that: this electrode is the some of luminous source device.
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| CN 03148262 CN1250451C (en) | 2003-06-30 | 2003-06-30 | Non-crystal diamond material and manufacturing method and application thereof |
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| CN101147426B (en) * | 2005-01-26 | 2010-10-06 | 宋健民 | EL device and EL method using the EL device |
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