CN105633263A - Carbon nanofiber/diamond composite thin-film material and application thereof as thermal battery energy conversion device - Google Patents
Carbon nanofiber/diamond composite thin-film material and application thereof as thermal battery energy conversion device Download PDFInfo
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Abstract
The invention discloses a carbon nanofiber/diamond composite thin-film material and an application thereof as a thermal battery energy conversion device. A diamond thin-film is deposited on an ordinary silicon wafer substrate by a microwave plasma technology; a silicon substrate is etched away by 20% KOH solution to prepare a self-supported diamond thin-film; a metal thin-film is deposited on the diamond thin-film by an electron beam evaporation-deposition method or a magnetron sputtering method; and a carbon nanofiber layer grows on the metal thin-film. The carbon nanofiber growing by the method has very high absorptivity within a near-total sunlight wave band, and can convert solar radiation energy into thermal energy; and a diamond thin-film substrate has good thermal conductivity, can quickly conduct the heat absorbed by the carbon nanofiber to a thermoelectric energy conversion material of a semiconductor, is integrated with a solar-thermal battery device and achieves high-efficiency solar-electrical energy conversion. The carbon nanofiber/diamond composite thin-film material has good industrial application prospect and basic scientific research value.
Description
Technical field
The present invention relates to composite preparation and thermal cell energy conversion device technical field, be specifically related to a kind of carbon nano-fiber/diamond composite film material and the application as thermal cell energy conversion device thereof.
Background technology
In recent years, along with the imbalance between energy resource supply and economic development highlights, worldwide energy crisis and environmental pollution are day by day serious, " carbon reduction " and to seek clean energy technology be that countries nowadays is without unconcerned subject under discussion. Solar energy is a kind of cleaning, the reproducible energy, has a wide range of applications and become desirable energy demand prediction in people's daily life, work. This is firstly the need of the form converted solar energy into as electric energy or heat energy, i.e. photovoltaic type and the conversion of photo-thermal type solar energy.
For general commercial silicon-based photovoltaic type solaode, due to the energy of incident photon with excite the relativeness of energy needed for silicon-based semiconductor carrier, the wavelength photon more than��1100nm can not be absorbed by silica-based solar cell, and a big chunk energy in short wavelength photons, except exciting efficient carrier, form with heat energy is lost, and electric energy can not be efficiently converted into. Wherein, there are about��incident photon energy of 19% can not be absorbed, can in absorbed incident photon energy��33% lose with the form of heat energy, unknown losses��15%, available solar energy��33%. In order to utilize solar energy, scientists to have developed baroque many node solar batteries (cost of manufacture is expensive) more fully. While it is true, still the solar energy of old significant proportion cannot be utilized, this part is mainly with form of thermal energy loss (infrared part and the heat-energy losses in photoelectric conversion process).
Traditional photo-thermal type solar electrical energy generation refers to by collecting solar thermal energy, provides steam by heat-exchanger rig, in conjunction with steam turbine generator technique, reaches generating purpose. Although the method can be substantially reduced cost for solar power generation and improve solar energy conversion efficiency, but generally requires the device systems of complexity so that application scenario is very restricted. In recent years, utilize high efficiency semi-conductor thermoelectric material directly to absorb solar energy (selective absorbing infrared band spectrum) carry out thermoelectric energy conversion or absorb photovoltaic solar cell cogeneration to improve solar conversion efficiency reduction cost of electricity-generating.
Thermoelectric material is a kind of functional semiconductor material that the energy of two kinds of different shapes of heat and electricity under not having the assistance of other specific external force or device, can be made mutually to change. Thermal cell is based on the device that semi-conductor thermoelectric material realizes heat energy and electric energy is directly changed mutually. Because of himself have firm in structure reliable, size is little, noiselessness, life-span length, pollution-free, the plurality of advantages such as be accurately controlled and cause the extensive concern of scientific circles and industrial quarters. Improve the solar energy thermal-to-electric energy transformation efficiency of thermal cell, it is necessary to the hot junction of thermal cell and cold end keep the temperature difference big as far as possible. The design factor of heat extraction electric material self outer (such as thermal conductivity), hot junction should be collected the emittance of sunlight as much as possible and pass to rapidly thermal cell; The waste heat of thermal cell should be quickly disseminated in the hot-fluid carrier of surrounding by cold end as far as possible, keeps relatively low temperature.
It would therefore be highly desirable to a kind of thermal cell energy conversion device of preparation, the heat absorbing end of this thermal cell and radiating end is made all to have higher thermal conductivity; Meanwhile, heat absorbing end will high efficiency as far as possible absorption solar energy, to reaching the highest thermoelectric energy conversion efficiency.
Summary of the invention
It is an object of the invention to provide a kind of carbon nano-fiber/diamond composite film material and the application as thermal cell energy conversion device thereof, it is prepared for carbon nano-fiber/diamond composite film material by chemical vapour deposition technique, and it can be used as the energy conversion device of thermal cell, while efficient absorption solar energy, possess again high thermal conductivity, reach the highest thermoelectric energy conversion efficiency.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of carbon nano-fiber/diamond composite film material, this composite film material includes diamond film layer, metal level and carbon nano-fiber layer, wherein: a side surface of described diamond film layer has groove structure, described deposition of metal is in the bottom land of described groove, and described carbon nano-fiber layer growth on the metal layer and is filled in described groove.
Thickness >=50 ��m of described diamond film layer, the thickness of described metal level is 20-50nm, and the thickness of described carbon nano-fiber layer is 5-10 ��m; Crystallite size >=50 ��m of described diamond film layer; Described carbon nano-fiber is linear carbon nano-fiber.
Described groove structure refers to that multiple groove parallel arrangement is in diamond film layer surface, and flute pitch is 20-30 ��m.
Described metal level is Cu, Fe, Ni or Co simple metal, or the alloy of Cu, Fe, Ni or Co.
Absorptivity >=99.5% of described carbon nano-fiber layer, the thermal conductivity of diamond film layer is more than 1000W/m K, carbon nano-fiber surface density 4��8g/m2, carbon nano-fiber/diamond composite film material is perpendicular to the thermal conductivity >=850W/m K in film surface direction.
The preparation method that the present invention also provides for above-mentioned carbon nano-fiber/diamond composite film material, the method comprises the steps:
(1) preparation of diamond film layer:
On at the bottom of the silicon wafer-based of polishing, with Chemical Vapor Deposition Diamond Films, being then immersed in the KOH solution that concentration is 20wt.% of 75 DEG C, after soaking 12 hours, stripping silicon chip substrate obtains self-supporting diamond thin film; Described chemical vapour deposition technique selects MPCVD method, and (microwave power is 500 watts-3500 watts, air pressure is 5-100Torr, methane content 1-10%, carrier gas is hydrogen) or hot filament CVD (filament temperature is 1800-2200K, air pressure is 5-30Torr, methane content 1-10%).
Its roughness at the bottom of the silicon wafer-based of described polishing, less than 5nm, silicon chip substrate thickness 300-500 ��m, preferably with the p/n type silicon chip of doping at the bottom of described silicon wafer-based, contributes to the growth of diamond.
(2) groove structure is prepared at diamond film surface;
(3) at groove bottom aggradation metal level: deposition process is electron beam evaporation-sedimentation, thermal evaporation or magnetron sputtering method;
(4) metal level grows carbon nano-fiber layer:
Carrying out the growth of carbon nano-fiber in CVD reaction chamber, growth conditions is: air pressure 500mbar, temperature 250 DEG C, growth time 10-20 minute; Reactor is evacuated to vacuum (1 �� 10 after terminating by growth-2Mbar), being warming up to 800 DEG C of annealing, annealing time is 1 hour, thus growing carbon nano-fiber layer on the metal layer and being filled in groove, it is thus achieved that described carbon nano-fiber/diamond composite film material.
Described carbon nano-fiber/diamond composite film material can as the energy conversion device of thermal cell, described thermal cell energy conversion device is the device with heat absorbing end and radiating end, and its heat absorbing end can absorb solar energy and be transferred to radiating end, then given the energy to the thermoelectric material of thermal cell by radiating end. When composite film material of the present invention is used for the energy conversion device of thermal cell, carbon nano-fiber layer absorbs sunlight and changes into after heat energy is transferred to diamond film layer, is transmitted further in thermal cell thermoelectric material and produces electric energy.
Described thermal cell is to be formed by two electrodes and the thermoelectric material that is arranged between two electrodes, and when assembling with described thermal cell energy conversion device, an electrode of thermal cell is as hotter side electrode, and another electrode is as cold terminal electrodes; The assembling mode of described energy conversion device and thermal cell is: using carbon nano-fiber layer as heat absorbing end, directly absorbs solar energy or absorbs heat by photovoltaic cell; Using diamond film layer as radiating end, and radiating end is connected with the hotter side electrode of thermal cell. (when contiguous block build thermal cell, diamond film layer is connected with the hotter side electrode of thermal cell by scolding tin, heat conduction elargol or heat conductive silica gel, or will on diamond film layer conductive metal deposition layer, then conductive metal layer is connected with the hotter side electrode of thermal cell by scolding tin; When connecting film type thermal cell, can on diamond thin the hotter side electrode of Direct precipitation thermal cell, then deposited thermoelectric materials.
Design philosophy of the present invention and having the beneficial effect that:
1, the polished silicon slice roughness of the substrate that the present invention uses when preparing diamond thin is less than 5nm, thickness 300-500 ��m. Use microwave plasma CVD or hot filament CVD, it is possible under comparatively gentle environment, the high-quality diamond thin of large area fast-growth. The p/n type silicon chip with doping is used to contribute to the growth of diamond thin. Use potassium hydroxide heat erosion method, can conveniently diamonds separated thin film and silicon base. It is integrated for further device that the High Quality Diamond Film of thickness >=50 ��m has enough mechanical properties.
2, the present invention on diamond film layer surface bottom portion of groove deposition metal level as growth carbon nano-fiber catalyst, thickness can it is preferred that. When thickness is less than 20nm, metallic film is discontinuous in island growth; When thickness is more than 50nm, would be likely to occur metal film one layer superfluous between the carbon nano-fiber and the substrate diamonds that grow on the metal layer, be unfavorable for the transmission of heat. On metal level, the carbon nano-fiber of growth has significantly high absorptivity (99.5%), stable performance; And diamond thin substrate prepared by the present invention has significantly high thermal conductivity (1500-2000W/m K), it is possible to the solar heat that carbon nano-fiber absorbs is transferred to rapidly thermo-electric converting material. Therefore, carbon nano-fiber/diamond composite film material is highly suitable as light-heat transfer/conveying material, improves optical and thermal efficiency of transmission.
3, carbon nano-fiber layer not only to absorb solar energy expeditiously and change into heat energy, and needs to pass out the heat energy of generation expeditiously, could further change into electric energy. Accordingly, it would be desirable to carbon fiber layer has higher photo-thermal conversion efficiency and heat conduction efficiency it is necessary to control the thickness of carbon nano-fiber layer and increase the carbon fiber layer contact area with diamond thin matrix to strengthen heat-conducting effect. Erode away groove structure at diamond surface and can increase the contact area of itself and carbon nano-fiber layer, the degree of depth of groove, chemical vapour deposition (CVD) temperature/time can regulate and control the thickness of carbon fiber layer. Experiment finds, when carbon nano-fiber layer thickness is more than 25 ��m, its heat conductivility sharply declines, the temperature difference caused by thermal resistance is more than 40 DEG C, the solar energy that carbon fiber layer absorbs can not effectively be transferred to thermoelectric material and produce electric energy after changing into heat energy, make solar energy-thermo-electrically conversion efficiency be substantially reduced. When carbon nano-fiber layer is crossed thin, its surface density declines, and Solar thermal conversion efficiency reduces. Consider that the thickness of the preferred carbon nano-fiber layer of factors above is at 5-10 �� m simultaneously.
4, after design above, the thermoelectric energy converting material of thermal cell and laminated film need to will not grow the side good contact of carbon nanocoils. During contiguous block build thermal cell, it is possible to directly use heat conduction elargol, high thermal conductive silicon glue or there is the scolding tin of special composition, the hotter side electrode (such as aluminum etc.) of thermal cell is connected with diamond thin; Or on diamond thin, first deposit one layer of conducting metal (such as chromium, gold, titanium, aluminum, silver etc.) by physical vaporous deposition, then be connected with thermal cell hotter side electrode with scolding tin etc., keep good contact. When connecting film type thermal cell, Available templates method is Direct precipitation metal electrode (hotter side electrode) and semi-conductor thermoelectric material on diamond thin successively; The cold terminal electrodes of thermal cell can adopt above-mentioned similar approach, and cold terminal electrodes has the silicon chip of 50-100nm diamond thin, silico briquette or the radiating end such as metal molybdenum sheet, molybdenum block to be connected with growth. Again through air-cooled or the cold terminal electrodes of thermal cell is maintained at relatively low temperature by the method for recirculated water cooling. Here insulation characterisitic and the high-termal conductivity of Diamond Thin Films Materials are still made full use of.
5, carbon nano-fiber/diamond laminated film can be used for the intermediate layer of photovoltaic/thermoelectricity composite battery, infrared band solar energy and the waste heat of photovoltaic cell generation that help thermal cell absorption photovoltaic cell can not absorb generate electricity, and improve the efficiency that optical and thermal-electric flux converts further.
Accompanying drawing explanation
Fig. 1 is the carbon nano-fiber/diamond composite film material structural representation of embodiment 1 preparation.
Fig. 2 is solar heat battery structure schematic diagram.
Fig. 3 is photovoltaic/thermoelectricity composite battery structural representation.
Fig. 4 solar spectral extraction and application schematic diagram.
In figure: 1-diamond thin; 2-metal level; 3-carbon nano-fiber layer; 4-thermal cell hotter side electrode; 5-thermoelectric material; 6-thermal cell cold terminal electrodes; The diamond thin that 7-is connected with thermal cell cold terminal electrodes; 8-thermal cell radiating end; 9-solaode.
Detailed description of the invention
Further explain and describe present invention below by way of detailed description of the invention, but embodiment is not to be construed as limiting the scope of the invention.
The present invention uses MPCVD method or hot filament CVD at the bottom of the silicon wafer-based of polishing on growing diamond membrane, it is possible to quickly, large scale, the high-quality diamond thin of growth. Use is adulterated, high conductivity silicon chip makes film substrate, contributes to alleviating the charge build-up problems in growth course, improves film quality. The quality of diamond thin is more good, and thermal conductivity is more high. The thermal conductivity of diamond thin increases with thickness and crystallite dimension and becomes big. When crystal particle scale is more than 5 ��m, when thickness is more than 20 ��m, its thermal conductivity is more than 1000W/m K. Simultaneously taking account of it and also should possess certain mechanical property, the diamond thin of��50 ��m has good toughness and tenacity, it is possible to the competent integrated work of further device. Hot potassium hydroxide toxicity is little, it is possible to safer erodes at the bottom of silicon wafer-based, prepares diamond self-supporting film. Diamond film after separation also needs with hot water, deionized water, acetone and alcohol washes.
Use magnetron sputtering or electron beam evaporation equipment, deposit one layer��20nm simple metal or alloy on self-supporting diamond thin film surface, if copper, ferrum, nickel etc. are as catalyst, grow carbon nano-fiber at diamond film surface. Can pass through to control the quantity of metal or alloy deposition, regulate the surface density of carbon nano-fiber. It was found that, blocked up carbon nano-fiber layer not only there is no obvious help for absorbing solar energy-thermal transition, and thermal resistance can be increased, reduce hot-fluid efficiency of transmission. It is therefore preferable that the thickness of carbon nano-fiber layer is at 5-10 ��m.
Although it was found that, carbon nano-fiber has good extinction effect, but due to the open structure of self, the heat conductivility of carbon nano-fiber layer is not good. The starting point of the present invention is based on the high thermal conductivity making full use of the carbon nano-fiber light-heat transfer characteristic close to all band solar spectrum and diamond thin, converts solar energy into heat and is quickly conducted to thermal cell generation electric energy. Therefore, for improving the heat conductivility of carbon nano-fiber layer, highdensity surface texture is etched at diamond surface, detailed description of the invention is as follows: 1. deposit one layer of ferrum on the diamond, the simple metal thin film of cobalt or nickel, thickness is 10-200nm, anneals 1��10 hour in a vacuum at 600-900 DEG C, by the width of the THICKNESS CONTROL groove structure of metal film, annealing time controls the degree of depth of groove structure; 2. placing one layer of cellular commercial aluminum dipping form version on diamond thin, utilize the mode of reactive ion etching, etch groove structure on the diamond, wherein, gash depth is determined by etch period, and width is determined by masterplate; 3., when preparing diamond, place one layer of anti-cellular commercial aluminum dipping form cellular diamond of version direct growth, the condition in growth conditions such as mode 1 at substrate surface, aluminum dipping form version is removed after terminating by growth, obtaining groove structure diamond, gash depth is determined by growth time, and width is determined by masterplate. Deposit the metal level catalyst as growth carbon nano-fiber on the surface of groove, again through controlling the required pattern of technological parameter growth and the carbon nano-fiber of thickness, increase the contact area of itself and diamond thin.
Embodiment 1
The present embodiment carbon nano-fiber/diamond composite film material preparation process is as follows:
(1) at the bottom of in the silicon wafer-based of polishing, MPCVD method is selected to prepare diamond thin, then being immersed in the KOH solution that concentration is 20wt.% of 75 DEG C, after soaking 12 hours, stripping silicon chip substrate obtains self-supporting diamond thin film; Described MPCVD method technological parameter is: microwave power is 3000 watts, and air pressure is 5-100Torr, and unstrpped gas is methane and hydrogen (carrier gas), methane content 10%. Silicon chip roughness of the substrate used, less than 5nm, silicon chip substrate thickness 300-500 ��m, preferably with the p/n type silicon chip of doping at the bottom of silicon wafer-based, contributes to the growth of diamond.
(2) groove structure is prepared at diamond film surface, flute pitch 20-30 ��m;
(3) adopt the copper film of magnetron sputtering method one layer of 20nm of sputtering at groove bottom land, this thin film was vacuum annealing 1 hour, and annealing temperature is about 500 DEG C;
(4) groove floor growth copper film sample carries out the growth of carbon nano-fiber in CVD reaction chamber, and growth conditions is: air pressure 500mbar, temperature 250 DEG C, growth time 20 minutes; Reactor is evacuated to vacuum to 1 �� 10 after terminating by growth-2Mbar, is warming up to 800 DEG C of annealing, and annealing time is 1 hour, thus growing carbon nano-fiber layer on the metal layer and being filled in groove, it is thus achieved that described carbon nano-fiber/diamond composite film material.
As shown in Figure 1, in carbon nano-fiber prepared by the present embodiment/diamond composite film material, one side surface of diamond film layer has groove structure, and layers of copper thick for 20nm is deposited on the bottom land of groove, and carbon nano-fiber layer growth on the metal layer and is filled in groove. The thickness of described carbon nano-fiber layer is 5-10 ��m; Crystallite size >=50 ��m of described diamond film layer; Described carbon nano-fiber is linear carbon nano-fiber.
Absorptivity >=99.5% of described carbon nano-fiber layer, the thermal conductivity of diamond film layer is more than 1000W/m K, carbon nano-fiber surface density 4��8g/m2, carbon nano-fiber/diamond composite film material is perpendicular to the thermal conductivity >=850W/m K in film surface direction.
Prepared carbon nano-fiber/diamond composite film material is applied to the energy conversion device of thermal cell, with the integrating process of thermal cell as in Figure 2-4:
Thermal cell by two electrodes and between thermoelectric material form, two one, electrodes are used for absorbing heat as hot junction battery, and another is used for, as cold terminal electrodes, the heat that sheds.
When composite film material of the present invention is used for the energy conversion device of thermal cell, carbon nano-fiber layer absorbs sunlight and changes into after heat energy is transferred to diamond film layer, is transmitted further in thermal cell thermoelectric material and produces electric energy. when assembling with described thermal cell energy conversion device, an electrode of thermal cell is as hotter side electrode, and another electrode is as cold terminal electrodes, the assembling mode of described energy conversion device and thermal cell is: using carbon nano-fiber layer as heat absorbing end, directly absorb solar energy (Fig. 2) or assembled the radiations heat energy (Fig. 3) absorbing solar energy by Fresnel Lenses, or by the infrared band (Fig. 4) in spectroscope separation solar spectral, using diamond film layer as radiating end, and radiating end is connected with the hotter side electrode of thermal cell. during contiguous block build thermal cell, heat conduction elargol (such as SPIInc.ConductiveSilverPaint) can be used, high thermal conductive silicon glue (Goh, T.J., Seetharamu, K.N., Quadir, G.A, Zainal, Z.A.&Ganeshamoorthy, K.J.Thermalinvestigationsofmicroelectronicschipwithnon-u niformpowerdistribution:temperaturepredictionandthermalp lacementdesignoptimization.MicroelectronicsInternational 21, 29-43, 2004) or there is the scolding tin of special composition, the hotter side electrode (aluminum or copper etc.) of thermal cell is connected with diamond thin, or on diamond thin, first deposit layer of metal (such as chromium, gold, titanium, aluminum, silver etc.) by Lithographic template method and physical vaporous deposition, then be connected with thermal cell hotter side electrode with scolding tin etc., keep good contact. when connecting film type thermal cell, Available templates method is Direct precipitation metal electrode (hotter side electrode) and p/n type semi-conductor thermoelectric material on diamond thin successively, such as Bi (Sb)-Te (Se) alloy system of commercial compositional. the cold terminal electrodes being sequentially connected with thermal cell again has the metal heat sink of diamond thin to be connected with growth.
The cold terminal electrodes of thermal cell can use the metal (copper, aluminum etc.) that heat conduction is good, as adopted the method that document describes to prepare (On-chipcoolingbysuperlattice-basedthin-filmthermoelectri cs, NatureNanotechnology, 4,235,2009). The cold terminal electrodes of thermal cell connects heat sink material (thermal cell radiating end) again, radiating end material can utilize insulating properties and the high-termal conductivity of diamond thin, namely growth is adopted to have��the silicon chip of 100nm diamond thin, silico briquette or metal molybdenum sheet, molybdenum block etc., it is connected with the cold terminal electrodes of thermal cell with scolding tin or heat-conducting glue again, keeps good contact. Radiating end can by air-cooled or the waste heat of thermal cell is derived by the method for recirculated water cooling.
Carbon nano-fiber of the present invention/diamond laminated film can be used for photovoltaic/thermoelectricity composite battery. When thermal cell contacts series connection use with photovoltaic cell direct physical, thermal cell can directly absorb the infrared band energy (when photovoltaic cell is relatively thin, part sunlight can penetrate) that photovoltaic cell can not absorb; Thermal cell can also utilize the waste heat (heat energy that the hot carrier relaxation process that high energy excites produces) produced during photovoltaic cell capable of generating power to generate electricity. Carbon nano-fiber/diamond composite film material can as the intermediate layer of photovoltaic/thermoelectricity composite battery, effectively absorb the waste heat energy of solar energy infrared band or photovoltaic cell and pass to thermal cell, improving the efficiency of optical and thermal-electric flux conversion devices further.
Product test
Solar energy optical-thermal voltage-to-current is tested
Method of testing: use xenon lamp to do light source simulation sunlight, use Keithley4200 semiconducting behavior tester record thermal cell voltage-current characteristic curve. Contrast the size identical thermal cell (hereinafter referred to as compound sample) applying carbon nanocoils/diamond laminated film during test, connect the thermal cell (hereinafter referred to as plain edition sample) of shaggy common copper sheet, connect the photo-thermal voltage-to-current performance of the ordinary hot battery (hereinafter referred to as graphite mould sample) scribbling graphite (white carbon black)/copper sheet. During test, the height of light source distance sample keeps certain, and incident optical power density is constant. The cold end of thermal cell by recirculated cooling water be maintained at 20 DEG C constant. The quantity of the thermal cell composition, size and the P/N type thermoelectric material that use in three kinds of samples is just the same, is commercial Bi (Sb)-Te type and Bi-Te (Se) type.
Test result: increase and inconspicuous using plain edition sample as reference state, the photo-thermal open-circuit voltage of graphite mould sample and peak power, respectively��3% and��10%; The photo-thermal open-circuit voltage of compound sample and peak power increase fairly obvious, respectively > 15% He > 50%.
Claims (10)
1. carbon nano-fiber/diamond composite film material, it is characterized in that: this composite film material includes diamond film layer, metal level and carbon nano-fiber layer, wherein: a side surface of described diamond film layer has groove structure, described deposition of metal is in the bottom land of described groove, and described carbon nano-fiber layer growth on the metal layer and is filled in described groove.
2. carbon nano-fiber according to claim 1/diamond composite film material, it is characterised in that: thickness >=50 ��m of described diamond film layer, crystallite size >=50 ��m of described diamond film layer; The thickness of described metal level is 20-50nm; The thickness of described carbon nano-fiber layer is 5-10 ��m, and described carbon nano-fiber is linear carbon nano-fiber.
3. carbon nano-fiber according to claim 1/diamond composite film material, it is characterised in that: described groove structure refers to that multiple groove parallel arrangement is in diamond film layer surface, and flute pitch is 20-30 ��m.
4. carbon nano-fiber according to claim 1/diamond composite film material, it is characterised in that: described metal level is Cu, Fe, Ni or Co simple metal, or metal level is the alloy of Cu, Fe, Ni or Co.
5. carbon nano-fiber according to claim 2/diamond composite film material, it is characterised in that: absorptivity >=99.5% of described carbon nano-fiber layer, the thermal conductivity of diamond film layer is more than 1000W/m K, carbon nano-fiber surface density 4��8g/m2, carbon nano-fiber/diamond composite film material is perpendicular to the thermal conductivity >=850W/m K in film surface direction.
6. carbon nano-fiber according to claim 1/diamond composite film material, it is characterised in that: the preparation method of this composite film material comprises the steps:
(1) preparation of diamond film layer:
On at the bottom of the silicon wafer-based of polishing, with Chemical Vapor Deposition Diamond Films, being then immersed in the KOH solution that concentration is 20wt.% of 75 DEG C, after soaking 12 hours, stripping silicon chip substrate obtains self-supporting diamond thin film;
(2) groove structure is prepared at diamond film surface;
(3) at groove bottom aggradation metal level: deposition process is electron beam evaporation-sedimentation, thermal evaporation or magnetron sputtering method;
(4) metal level grows carbon nano-fiber layer:
Carrying out the growth of carbon nano-fiber in CVD reaction chamber, growth conditions is: air pressure 500mbar, temperature 250 DEG C, growth time 10-20 minute; Reactor is evacuated to 1 �� 10 after terminating by growth-2Mbar, is warming up to 800 DEG C of annealing, and annealing time is 1 hour, thus growing carbon nano-fiber layer on the metal layer and being filled in groove, it is thus achieved that described carbon nano-fiber/diamond composite film material.
7. carbon nano-fiber according to claim 6/diamond composite film material, it is characterised in that: in step (1), described chemical vapour deposition technique selects MPCVD method or hot filament CVD; In described MPCVD method: microwave power is 500-3500 watt, air pressure is 5-100Torr, and unstrpped gas is methane and hydrogen, methane content 1-10vol.% in unstrpped gas; In described hot filament CVD: filament temperature is 1800-2200K, air pressure is 5-30Torr, and unstrpped gas is methane and hydrogen, methane content 1-10vol.% in unstrpped gas.
8. carbon nano-fiber according to claim 6/diamond composite film material, it is characterized in that: in step (1), its roughness at the bottom of the silicon wafer-based of described polishing, less than 5nm, silicon chip substrate thickness 300-500 ��m, is the p/n type silicon chip with doping at the bottom of described silicon wafer-based.
9. using the application as the energy conversion device of thermal cell of the composite film material described in claim 1, it is characterized in that: using the described carbon nano-fiber/diamond composite film material energy conversion device as thermal cell, the carbon nano-fiber layer of this energy conversion device absorbs sunlight and changes into after heat energy is transferred to diamond film layer, is transmitted further in thermal cell thermoelectric material and produces electric energy.
10. carbon nano-fiber according to claim 9/diamond composite film material is as the application of thermal cell energy conversion device, it is characterized in that: described thermal cell is to be formed by two electrodes and the thermoelectric material that is arranged between two electrodes, when assembling with described thermal cell energy conversion device, one electrode of thermal cell is as hotter side electrode, and another electrode is as cold terminal electrodes; The assembling mode of described energy conversion device and thermal cell is: using carbon nano-fiber layer as heat absorbing end, directly absorbs solar energy or absorbs heat by photovoltaic cell; Using diamond film layer as radiating end, and by the connection of Dielectric film layers realization with the hotter side electrode of thermal cell.
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| CN113088921A (en) * | 2021-04-13 | 2021-07-09 | 昆明理工大学 | Preparation method of porous diamond film/three-dimensional carbon nanowire network composite material and product thereof |
| CN114383326A (en) * | 2022-01-11 | 2022-04-22 | 北京理工大学 | Photo-thermal transducer with gravity center supporting structure |
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