CN101246050B - Diamond compound film piece used for absolute bolometer and method for producing the same - Google Patents
Diamond compound film piece used for absolute bolometer and method for producing the same Download PDFInfo
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- CN101246050B CN101246050B CN2008100505000A CN200810050500A CN101246050B CN 101246050 B CN101246050 B CN 101246050B CN 2008100505000 A CN2008100505000 A CN 2008100505000A CN 200810050500 A CN200810050500 A CN 200810050500A CN 101246050 B CN101246050 B CN 101246050B
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Abstract
The present invention relates to a radiation-absorbing heat exchange sheet material on the absolute bolometer for measuring the solar radiation, especially to a diamond composite film used on the absolute bolometer and the preparing method thereof. The diamond composite film used on the absolute bolometer in the invention is prepared by compounding the pure diamond piece layer which is taken as the heat sink material and the black boron-doping diamond film that is taken as the light radiation absorbing material. The preparing method is firstly preparing the heat sink diamond piece with a one-time chemical vapor deposition, and then depositing the carbon nano-tube film layer on the diamond piece with a floating catalytic method. The diamond composite film of the invention has the advantages of strong heat and impact resistance, higher absorbing rate to the radiation and the rate is up to 99%, and stability for a long period; and the surface adhesions of the heat sink material and radiation-absorbing material are excellent. Thereby the measuring precision and sensitiveness of the bolometer can be increased and the measuring period can be shortened, and the adaptability of the absolute bolometer in the working condition of satellite is increased.
Description
Technical field
The present invention relates to absorbed radiation on a kind of absolute measuring bolometer that is used on the satellite measuring solar radiation and diamond compound film sheet of heat interchange sheet material, particularly a kind of absorbed radiation and preparation method thereof.
Background technology
In order to study earth radiation budget and energy circulation and, to need accurately to measure and the long term monitoring solar irradiance to the influence of global environment and climate change.Being used for observing the instrument of solar irradiance on satellite is the absolute measuring bolometer, needs the black absorption radiative material to come radiation is absorbed on the absolute measuring bolometer of measuring solar irradiance.The absolute measuring bolometer is placed on the weather satellite to be observed, and this just requires black absorption radiative material and the heat sink material on the absolute radiometer not only will be in conjunction with tight, good mechanical property, and will have high thermal conductivity and ultraviolet irradiation changes little.Before the present invention, the black absorption radiative material that is used on the electric calibration absolute radiometer is pitch-dark for being coated with the skim direct reflection with silver-colored conical cavity of the thin-walled of electroplating technology special facture and inner cavity surface, and heat sink material is the metal aluminum barrel.The thermal conductivity of this different materials is not too high, the associativity that reflects pitch-dark and silver-colored chamber is not high, and reflecting the pitch-dark ultraviolet ray irradiation back that is subjected to for a long time on satellite can reduce gradually to the absorptivity of radiation, this all can influence the measurement of absolute radiometer to solar irradiance, causes the measuring accuracy of radiometer to reduce, sensitivity is low and Measuring Time is long.
Summary of the invention
The objective of the invention is in order to solve at present in measuring radiation equipment, as monitor the shortcoming that absorbed radiation heat exchange material used on the absolute measuring bolometer of solar irradiance exists, a kind of diamond compound film sheet and preparation method thereof that is used on the absolute measuring bolometer is proposed, to improve the measuring accuracy and the serviceable life of absolute measuring bolometer.
The present invention is used for the diamond compound film sheet on the absolute measuring bolometer, is by being composited as the pure diamond lamella of heat sink material with as the carbon nano-tube rete of optical radiation absorbing material, and described adamas lamella is that thermal conductivity 〉=15W/Kcm, resistivity are 10
13～10
15The water white transparency diaphragm of Ω cm; Described carbon nano-tube rete is the tubular structure that becomes the key interconnection to form by carbon atom, is evenly distributed on the described adamas lamella, and the thermal conductivity of carbon nano-tube rete is that 7～10W/Kcm, resistivity are 10
9～10
13Ω cm.
The diameter of described carbon nano-tube is that 2nm～200nm, length are 50nm～10 μ m, is orderly orthogonal array or unordered horizontally-arranged distribution.
Preparation method's process of diamond compound film sheet of the present invention is as follows.
A. in MW-PCVD microwave plasma CVD system equipment, with H
2And CH
4Make stock media, the metal molybdenum sheet is made substrate, under following process conditions, carry out a chemical vapor deposition and prepare water white diamond chip:
H
2Flow is 200sccm, CH
4Flow is 1～3sccm, and microwave power is 3.8～4.2KW, and deposition pressure is 11～17KPa, and underlayer temperature is 750～950 ℃.About 1～3 μ m/h of growth rate.Thermal conductivity 〉=the 15W/Kcm of the diamond film of preparation, its resistivity is 10
13～10
15Ω cm, 0.4mm is thick, is colourless transparent film.
B. the diamond chip that a step is obtained carries out grinding and polishing, and making one side surface roughness is 50～100nm, and the opposite side surfaceness is＜40nm;
C. the diamond chip after will polishing cuts into required geomery;
D. the diamond chip after the cutting is carried out following surface preparation, soak more than 30 minutes with chromic acid solution earlier, use deionized water rinsing then, promptly removed impurity and the grease on the diamond chip, be placed in the acetone soln ultrasonic cleaning again 15 minutes, placed the alcoholic solution ultrasonic cleaning again 15 minutes; Place deionized water for ultrasonic to clean at last 15 minutes, place on 150 ℃ of hot plates and dry;
E. on being the side of 50～100nm, the surfaceness of the diamond chip after the above-mentioned processing carries out floating catalytic method deposition of carbon nanotubes rete, being grown in the horizontal pipe furnace of carbon nano-tube film carried out, the quartz boat that at first will fill the diamond chip of above-mentioned processing places the quartz ampoule middle part, and the quartz ampoule oral area is placed the ferrocene catalyzer; Temperature rise period, reaction chamber is by N
2Gas shiled, controlling its flow is 50～60sccm; When temperature reaches 700～800 ℃, feed C
2H
2Gas is controlled C simultaneously
2H
2The flow of gas is 30～40sccm, N
2Flow control be 150～200sccm, the ferrocene quality control is 0.45～0.75g; Deposition is closed C after finishing
2H
2, quartz ampoule is at N
2Cool to room temperature under the atmosphere, cooling stage control N
2Flow is 50sccm.
The described metal molybdenum substrate of step a carries out pre-service: ground 15 minutes sonicated 10 minutes in acetone soln then, sonicated 10 minutes in alcoholic solution again with diamond paste in the following manner before the heat sink diamond chip of vapour deposition.
The grinding and polishing of the described diamond chip of step b is to adopt the surface chemistry etching earlier, and mechanical lapping polishing then is to the diamond film twin polishing.
The described diamond chip cutting of step c is to adopt the YAG laser cutting technique that diamond chip is carried out the high precision cutting,
The described chromic acid solution of steps d is Cr
2O
3Be dissolved in resulting saturated solution behind the concentrated sulphuric acid.
Diamond compound film sheet of the present invention, as the adamas lamella of heat sink material and strong as the carbon nano-tube film surface adhesion of optical radiation absorbing material, absorptivity changes little after the absorption layer raying, absorptivity to radiation is higher, reach 99%～99.1%, improved adaptability and the serviceable life of absolute radiometer under the condition of work on the satellite, the measuring accuracy and the sensitivity that have improved radiometer, shorten measuring period.
Description of drawings
Fig. 1 is the carbon nano-tube film surface form of diamond compound film sheet of the present invention.
Embodiment
By the following examples the inventive method is further elaborated.
Embodiment 1
A kind of diamond compound film sheet that is used on the absolute measuring bolometer is by being composited as the pure diamond lamella of heat sink material with as the carbon nano-tube rete of optical radiation absorbing material, and described adamas lamella is that thermal conductivity 〉=15W/Kcm, resistivity are 10
13～10
15The water white transparency diaphragm of Ω cm; Described carbon nano-tube rete is the tubular structure that becomes the key interconnection to form by carbon atom, is evenly distributed on the described adamas lamella, and the thermal conductivity of carbon nano-tube rete is that 7～10W/Kcm, resistivity are 10
9～10
13Ω cm.
Concrete preparation process is as follows:
(1) heat sink diamond chip of chemical vapor deposition.Heat sink diamond film is to adopt MW-PCVD microwave plasma CVD systems produce, and it belongs to the electrodless discharge method, than obtaining the high high-purity transparent diamond film of quality under the infrabar.Substrate adopts the metal molybdenum plate during deposition, and Method of processing a substrate is to adopt diamond paste to grind 30 minutes, uses acetone, each sonicated of alcohol 10 minutes then.Hydrogen and methane all are by mass flowmeter Control Flow, H
2Flow is 200sccm, CH
4Flow is 3sccm, and microwave power is 4.2KW, and deposition pressure is 11KPa, and underlayer temperature is 850 ℃, the about 3 μ m/h of growth rate.The thermal conductivity of the adamas diaphragm of preparation is 15W/Kcm, and its resistivity is 10
13Ω cm, 0.4mm is thick, is colourless transparent film.
(2) grinding and polishing diamond heat-sink sheet.Since metal molybdenum and adamas ask difference on the bigger thermal expansivity of existence, therefore diamond film is easy to break away from automatically from substrate in cooling procedure and becomes the disk of self-supporting, adopt the diamond film with MW-PCVD preparation method that the surface chemistry etching combines with mechanical polishing and grinding to the diamond film twin polishing then, the roughness that makes a side surface of diamond chip is 50～100nm (rms), the roughness on opposite side surface is less than 40nm (rms), and thickness is between 0.3～0.4mm.
(3) cutting diamond heat-sink sheet.Adopt the YAG laser cutting technique that diamond film is carried out the high precision cutting, reach required design size.
(4) surface preparation of heat sink diamond chip.Be heated to 300 ℃ with the chromic acid immersion earlier, be 50 minutes heat time heating time, and used chromic acid is Cr
2O
3Be dissolved in resulting saturated solution behind the concentrated sulphuric acid; Use a large amount of deionized water rinsings immediately, removed impurity and grease on heat sink like this; Placed the acetone soln ultrasonic cleaning then 15 minutes; Placed the alcohol ultrasonic cleaning again 15 minutes; Place deionized water for ultrasonic to clean at last 15 minutes, place on 150 ℃ of hot plates and dry.
(5) on being the side of 50～100nm, the surfaceness of the diamond chip after the above-mentioned processing carries out floating catalytic method deposition of carbon nanotubes rete.
Being grown in the horizontal pipe furnace of carbon nano-tube film carried out, and the quartz boat that at first will fill the heat sink diamond chip of above-mentioned processing places the quartz ampoule middle part, and the ferrocene catalyzer places the quartz ampoule oral area, and the temperature rise period, reaction chamber is by N
2Protection, controlling its flow is 60sccm; When temperature of reaction reaches 700 ℃, feed C
2H
2Gas is controlled C simultaneously
2H
2The flow of gas is 30sccm, N
2Flow control be 150sccm, the ferrocene quality control is at 0.45g.Reaction is closed C after finishing
2H
2, quartz ampoule is at N
2Cool to room temperature under the atmosphere, control N
2Flow is 50sccm.Used C in the experiment
2H
2And N
2Purity all more than 99.5%.The control reaction time is 30 minutes, and the thickness that makes boron-doping black diamond film is between 200nm～30 μ m.
The black carbon nanotube is the tubular structure that becomes the key interconnection to form by carbon atom, diameter range: 2nm～200nm, length range: 50nm～10 μ m.Even carbon nanotube is distributed on the heat sink diamond chip, and the distribution of carbon nano-tube is orderly orthogonal array.The thermal conductivity of black carbon nanotube films is 7W/Kcm, and its resistivity is 10
13Ω cm, roughness is 50nm～25 μ m, thickness is between 200nm～30 μ m.
Embodiment 2
Prepare the diamond compound film sheet that is used on the absolute measuring bolometer by embodiment 1 same method step, its difference only is:
The process conditions of (1) heat sink diamond chip of chemical vapor deposition are: H
2Flow is 200sccm, CH
4Flow is 1sccm, and microwave power is 3.8KW, and deposition pressure is 17KPa, and underlayer temperature is 950 ℃, the about 1 μ m/h of growth rate.The thermal conductivity of the adamas diaphragm that is obtained is that 18W/Kcm, resistivity are 10
15Ω cm.
(2) process conditions of floating catalytic method deposition of carbon nanotubes rete are: the temperature rise period, reaction chamber is by N
2Protection, controlling its flow is 55sccm; When temperature of reaction reaches 800 ℃, feed C
2H
2Gas is controlled C simultaneously
2H
2The flow of gas is 35sccm, N
2Flow control be 200sccm, the ferrocene quality control is at 0.6g.Reaction is closed C after finishing
2H
2, quartz ampoule is at N
2Cool to room temperature under the atmosphere, control N
2Flow is 50sccm.Used C in the experiment
2H
2And N
2Purity all more than 99.5%.The control reaction time is 25 minutes, and the thickness that makes boron-doping black diamond film is between 200nm～30 μ m.
The black carbon nanotube is the tubular structure that becomes the key interconnection to form by carbon atom, diameter range: 2nm～200nm, length range: 50nm～10 μ m.Even carbon nanotube is distributed on the heat sink diamond chip, and the distribution of carbon nano-tube is that orderly orthogonal array is mixed with unordered horizontally-arranged.The thermal conductivity of black carbon nanotube films is 9W/Kcm, and its resistivity is 10
12Ω cm, roughness is 50nm～25 μ m, thickness is between 200nm～30 μ m.
Embodiment 3
Prepare the diamond compound film sheet that is used on the absolute measuring bolometer by embodiment 1 same method step, its difference only is:
The process conditions of (1) heat sink diamond chip of chemical vapor deposition are: H
2Flow is 200sccm, CH
4Flow is 2sccm, and microwave power is 4KW, and deposition pressure is 13KPa, and underlayer temperature is 750 ℃, the about 2 μ m/h of growth rate.The thermal conductivity of the diamond chip of preparation is 17W/Kcm, and its resistivity is 10
14Ω cm.
(2) process conditions of floating catalytic method deposition of carbon nanotubes rete are: the temperature rise period, reaction chamber is by N
2Protection, controlling its flow is 50sccm; When temperature of reaction reaches 800 ℃, feed C
2H
2Gas is controlled C simultaneously
2H
2The flow of gas is 40sccm, N
2Flow control be 170sccm, the ferrocene quality control is at 0.75g.Reaction is closed C after finishing
2H
2, quartz ampoule is at N
2Cool to room temperature under the atmosphere, control N
2Flow is 50sccm.Used C in the experiment
2H
2And N
2Purity all more than 99.5%.The control reaction time is 25 minutes, and the thickness that makes boron-doping black diamond film is between 200nm～30 μ m.
The black carbon nanotube is the tubular structure that becomes the key interconnection to form by carbon atom, diameter range: 2nm～200nm, length range: 50nm～10 μ m.Even carbon nanotube is distributed on the heat sink diamond chip, and the distribution of carbon nano-tube is unordered horizontally-arranged.The thermal conductivity of black carbon nanotube films is 10W/Kcm, and its resistivity is 10
13Ω cm, roughness is 50nm～25 μ m, thickness is between 200nm～30 μ m.
Claims (7)
1. diamond compound film sheet that is used on the absolute measuring bolometer, it is characterized in that, by being composited as the pure diamond lamella of heat sink material with as the carbon nano-tube rete of optical radiation absorbing material, described adamas lamella is that thermal conductivity 〉=15W/Kcm, resistivity are 10
13～10
15The water white transparency diaphragm of Ω cm; Described carbon nano-tube rete is the tubular structure that becomes the key interconnection to form by carbon atom, is evenly distributed on the described adamas lamella, and the thermal conductivity of carbon nano-tube rete is that 7～10W/Kcm, resistivity are 10
9～10
13Ω cm.
2. the diamond compound film sheet that is used on the absolute measuring bolometer according to claim 1 is characterized in that, the diameter of described carbon nano-tube is that 2nm～200nm, length are 50nm～10 μ m, is orderly orthogonal array or unordered horizontally-arranged distribution.
3. described preparation method who is used for the diamond compound film sheet on the absolute measuring bolometer of claim 1 is characterized in that may further comprise the steps:
A. in MW-PCVD microwave plasma CVD system equipment, with H
2And CH
4Make unstrpped gas, the metal molybdenum sheet is made substrate, under following process conditions, carry out a chemical vapor deposition and prepare water white diamond chip: H
2Flow is 200sccm, CH
4Flow is 1～3sccm, and microwave power is 3.8～4.2KW, and deposition pressure is 11～17KPa, and underlayer temperature is 750～950 ℃;
B. the diamond chip that a step is obtained carries out grinding and polishing, and making one side surface roughness is 50～100nm, and the opposite side surfaceness is less than 40nm;
C. the diamond chip after will polishing cuts into required geomery;
D. the diamond chip after the cutting is carried out following surface preparation, soak more than 30 minutes with chromic acid solution earlier, use deionized water rinsing then, promptly removed impurity and the grease on the diamond chip, be placed in the acetone soln ultrasonic cleaning again 15 minutes, placed the alcoholic solution ultrasonic cleaning again 15 minutes; Place deionized water for ultrasonic to clean at last 15 minutes, place on 150 ℃ of hot plates and dry;
E. on being the side of 50～100nm, the surfaceness of the diamond chip after the above-mentioned processing carries out floating catalytic method deposition of carbon nanotubes rete, being grown in the horizontal pipe furnace of carbon nano-tube film carried out, the quartz boat that at first will fill the diamond chip of above-mentioned processing places the quartz ampoule middle part, and the quartz ampoule oral area is placed the ferrocene catalyzer; Temperature rise period, reaction chamber is by N
2Gas shiled, controlling its flow is 50～60sccm; When temperature reaches 700～800 ℃, feed C
2H
2Gas is controlled C simultaneously
2H
2The flow of gas is 30～40sccm, N
2Flow control be 150～200sccm, the ferrocene quality control is 0.45～0.75g; Deposition is closed C after finishing
2H
2, quartz ampoule is at N
2Cool to room temperature under the atmosphere, cooling stage control N
2Flow is 50sccm.
4. the preparation method who is used for the diamond compound film sheet on the absolute measuring bolometer according to claim 3, it is characterized in that the described metal molybdenum substrate of step a, before the heat sink diamond chip of vapour deposition, carry out pre-service in the following manner: ground 15 minutes with diamond paste, sonicated 10 minutes in acetone soln then, sonicated 10 minutes in alcoholic solution again.
5. the preparation method who is used for the diamond compound film sheet on the absolute measuring bolometer according to claim 3, the grinding and polishing that it is characterized in that the described diamond chip of step b is to adopt the surface chemistry etching earlier, mechanical lapping polishing then is to the diamond film twin polishing.
6. the preparation method who is used for the diamond compound film sheet on the absolute measuring bolometer according to claim 3 is characterized in that the described diamond chip cutting of step c is to adopt the YAG laser cutting technique that diamond chip is carried out the high precision cutting,
7. the preparation method who is used for the diamond compound film sheet on the absolute measuring bolometer according to claim 3 is characterized in that the described chromic acid solution of steps d is Cr
2O
3Be dissolved in resulting saturated solution behind the concentrated sulphuric acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100505000A CN101246050B (en) | 2008-03-18 | 2008-03-18 | Diamond compound film piece used for absolute bolometer and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100505000A CN101246050B (en) | 2008-03-18 | 2008-03-18 | Diamond compound film piece used for absolute bolometer and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| CN101246050A CN101246050A (en) | 2008-08-20 |
| CN101246050B true CN101246050B (en) | 2011-05-18 |
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|---|---|---|---|
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100552396C (en) * | 2008-03-18 | 2009-10-21 | 中国科学院长春光学精密机械与物理研究所 | Absorbed radiation composite diamond heat-exchanging diaphragm and preparation method thereof |
| CN105695831B (en) * | 2016-03-21 | 2017-10-31 | 中南大学 | A kind of continuous diamond framework enhancing composite of super-high heat-conductive and preparation method |
| CN105779805B (en) * | 2016-03-21 | 2017-10-31 | 中南大学 | Foam diamond framework strengthens Cu-base composites and preparation method |
| CN105733191B (en) * | 2016-03-21 | 2018-10-09 | 中南大学 | Different dimensions highly heat-conductive material enhances polymer matrix composite and preparation method |
| CN105671354B (en) * | 2016-03-21 | 2017-11-07 | 中南大学 | A kind of foam diamond framework reinforced aluminum matrix composites and preparation method thereof |
| CN112981364B (en) * | 2021-02-05 | 2022-08-02 | 北京科技大学 | Quick thermal response ultra-black material and preparation method thereof |
| CN113088921B (en) * | 2021-04-13 | 2023-03-24 | 昆明理工大学 | Preparation method of porous diamond film/three-dimensional carbon nanowire network composite material and product thereof |
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