CN1443870A - Method for preparing high photoconductive gain carbon nitride film - Google Patents
Method for preparing high photoconductive gain carbon nitride film Download PDFInfo
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- CN1443870A CN1443870A CN 03116464 CN03116464A CN1443870A CN 1443870 A CN1443870 A CN 1443870A CN 03116464 CN03116464 CN 03116464 CN 03116464 A CN03116464 A CN 03116464A CN 1443870 A CN1443870 A CN 1443870A
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- ion beam
- carbon nitride
- nitride films
- nitrogen
- photoconductive gain
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Abstract
The present invention adopts ion beam sputtering process to prepare carbon nitride film. It uses high-purity graphite as target material, uses the high-purity nitrogen gas as working gas of kaufman ion beam source, and its working gas pressure is 2-6X10 to the minus second. Said invention only uses the nitrogen gas as reactino and sputtering gas, and the film is aloof from direct bambardnment of concentrated nitrogen ion beam, so that the density of dangling bond compound defect can be reduced, and the possivation process of the hydrogen gas can be saved, under the AM1.5, 100m W/sq.cm standard light intensity the ratio value of photoconduction grain and dark conduction of the obtained carbon nitride film can be up to 10 to the sixth power.
Description
Technical field
What the present invention relates to is a kind of method for manufacturing thin film, and particularly a kind of high photoconductive gain carbon nitride films preparation method belongs to field of semiconductor materials.
Background technology
The eighties, scholar's theoretical prediction of Harvard University the carbon nitride films (β-C of beta structure
3N
4) because its short C-N covalent linkage, this material may have the hardness more taller than diamond.The scientist of countries in the world is in the method for making great efforts to seek synthetic this superhard novel material, but almost none success.The carbon nitride films that most studies person obtained is the structure of amorphous, has microparticle β-C in the film that the research of minority obtains
3N
4, these materials all do not have the superhard result of scholar's expection of Harvard University.,, it has been found that amorphous carbon nitride films has the optics and the electrical properties of many uniquenesses in photoelectric material and device application field in the Another application field.Have low-down work function as it, be available as the upper layer (as plasma display) of electron emission device; It has certain photoconductive gain, can be used on the opto-electronic device; Its optical energy gap can be adjusted in 2.5～0.5eV scope, can be used on the device of modulated optical band gap.Find by literature search, Takada, N. and Arai, K. wait the people on Applied Surface Science " applied surface science " magazine, to deliver one piece of article " Preparation and properties ofreactive-sputtered amorphous CNx films " (luxuriant and rich with fragrance brilliant carbon nitride films of reactive sputter-deposition and property research) (Vol.113, April 1997, P274 ~ 277), this article has been reported the character of the carbon nitride films that adopts the reactive sputtering process preparation, with argon and nitrogen is reaction and sputter gas, sedimentary film is a non-crystal structure, and photoconductive gain reaches 10
3What this technology adopted is argon and nitrogen mixture body sputtering technology, when sinking film, film is subjected to the high energy argon plasma and directly bombards, and introduces highdensity dangling bonds complex defect in film, in order to obtain high photoconductive gain, have to adopt hydrogen that film is carried out passivation.
Summary of the invention
The objective of the invention is to overcome the deficiency in the deposition technique that has carbon nitride films now, the high photoconductive gain carbon nitride films preparation method who uses on a kind of solar photovoltaic device is provided, be that nitrogen is the reactive ion beam sputtering technology of working gas, make it overcome disadvantages of background technology, obtaining tangible progress aspect the preparation technology of high photoconductive gain carbon nitride films and the equipment.
The present invention is achieved by the following technical solutions, and the inventive method adopts ion beam sputtering process to prepare carbon nitride films, and high purity graphite is as target, and high pure nitrogen is as the working gas of Kaufman (Kaufman) ion beam source, and operating air pressure is 2～6 * 10
-2Pa.
Below the inventive method is further described, concrete steps are as follows:
One, substrate cleans: the surface of adopting semi-conductor cleaning of the conventional end to carry out substrate is just cleaned, and substrate is placed on uses ultrasonic cleaning in the deionized water again, and with the ionized water flushing for several times, nitrogen dries up.
Two, settle substrate: the target body of target, Kaufman ion beam source, and film substrate form certain relative position, the target surface of target body becomes 45 to spend constant cant angle with horizontal plane, film substrate becomes the θ angle with the weight line.Adopt the high energy nitrogen ion beam to plunder the surface of penetrating the bombardment film, with the carbon nitride films of carbon ion reaction with the acquisition high nitrogen-containing, grazing angle is the θ angle, and the span at θ angle is 0 degree～20 degree.Target body is constantly cooled off by recirculated water.Film substrate can also can be utilized in heavy membrane process the temperature that film substrate raises because of the ionic bombardment by heater heats to 100 ℃～500 ℃.
Three, vacuumize and distribution: adopt mechanical pump to take out rough vacuum, diffusion pump pumping high vacuum, base vacuum finally reach 1 * 10
-4Pa pressure.By the input flow rate of mass flowmeter and noticeable degree nitrogen, the pressure of control reaction chamber is 2 * 10
-2～6 * 10
-2Pa.
Four, open the Kaufman ion source: the Kaufman ion beam source is a kind of divergence form ion source, and it generates ionic fluid in vacuum chamber, and the Kaufman ion source can generate ionic current and speeding-up ion stream directive target body.High-octane ion directly bombards target body, and the target body material is hit with forms such as ion, atom or atomic groups.This kind particulate splashes on the matrix of side with high-energy once more, is deposited on the surface of matrix.Adopting high purity graphite is the target body material, and high-purity nitrogen is the working gas and the sputter gas of ion beam source.Nitrogen passes through gas meter, send in the ion source through vacuum pipe, here the nitrogen ion beam of Chan Shenging has two effects, first, as reactive ion beam, for the generation of carbon nitride films provides the nitrogen ion source of participating in reaction, second, as the plasma sputter bundle, provide the nitrogen ion shell of bombardment target.Vacuum chamber was vacuumized by mechanical pump and diffusion pump in the 3rd step, and sent into reactant gases by gas meter.Can adopt one or two Kaufman ion beam source, if Kaufman ion beam source, then this Kaufman ion beam source (Kaufman) is a kind of divergence form ion source, the ionic fluid that it produced is both as reactive ion beam, for the generation of carbon nitride films provides the nitrogen ion of participating in reaction, again as the plasma sputter bundle.If two Kaufman ion beam sources, then one provides the plasma sputter bundle, and another provides the required reactive ion beam of generation of carbon nitride films.
Five, cvd nitride carbon film: Kaufman ion source ion beam intensity of flow is 30～80mA/cm
2Between adjustable, the beam energy of ionic fluid is that 300～800eV is adjustable, the line stability be (± 1.0%/h), acceleration voltage changes in 100V～500V, depositing time is 1～3 hour.
Six, photoconductive gain test: be to the photoconductive testing method that sedimentary film carried out, adopt the dark conductance of Keithley (Keithley company) source table MEASUREMENTS OF THIN and the electricity of illumination to lead, calculate photoconductive gain with following formula then: (electricity of illumination is led-dark conductance)/dark conductance.
The present invention has substantive distinguishing features and marked improvement, the present invention adopts ion beam sputtering process, only use nitrogen as reaction and sputter gas, and film is away from the direct bombardment of dense nitrogen ion beam, reduced the density of dangling bonds complex defects, saved the passivating process of hydrogen, at AM1.5,100mW/cm
2Under the etalon optical power, the photoconductive gain of the carbon nitride films that is obtained, the ratio of (electricity of illumination is led-dark conductance) and dark conductance can reach 10
6, can be used on the photovoltaic device, as the novel photovoltaic film material of photoactivation layer.
Embodiment
Embodiment one
Adopt a Kaufman ion beam source ionic fluid, nitrogen is working gas, and beam intensity is 30mA/cm
2, the ion beam stream energy is 800eV, and acceleration voltage is 100V, and film substrate 3 is angled 8 degree with the weight line, and operating air pressure is 2 * 10
-2Pa, film substrate is by heater heats to 100 ℃, and the heavy film time is 80 minutes.Sedimentary film is tested, and photoconductive gain reaches 10
3
Embodiment two
Adopt a Kaufman ion beam source ionic fluid, nitrogen is working gas, and the beam intensity of ionic fluid is 50mA/cm
2, the ion beam stream energy is 500eV, and acceleration voltage is 300V, and film substrate and weight line are angled 10 degree, and operating air pressure is 4 * 10
-2Pa, film substrate is by heater heats to 300 ℃, and the heavy film time is 60 minutes.Sedimentary film is tested, and photoconductive gain reaches 10
4
Embodiment three
Adopt a Kaufman ion beam source ionic fluid, nitrogen is working gas, and the beam intensity of ionic fluid is 80mA/cm
2, the ion beam stream energy is 300eV, and acceleration voltage is the 500V film, and substrate and weight line are angled 12 degree, and operating air pressure is 6 * 10
-2Pa, film substrate is by heater heats to 500 ℃, and the heavy film time is 120 minutes.Sedimentary film is tested, and photoconductive gain reaches 10
5
Embodiment four
Adopt a Kaufman ion beam source ionic fluid, nitrogen is working gas, and the beam intensity of ionic fluid is 50mA/cm
2, the ion beam stream energy is 500eV, and acceleration voltage is the 300V film, and substrate and weight line are angled 10 degree, and operating air pressure is 4 * 10
-2Pa does not carry out artificial heating, and the heavy film time is 60 minutes.Sedimentary film is tested, and photoconductive gain reaches 10
5
Claims (9)
1, a kind of high photoconductive gain carbon nitride films preparation method is characterized in that: adopt ion beam sputtering process to prepare carbon nitride films, high purity graphite is as target, and high pure nitrogen is as the working gas of Kaufman ion beam source, and operating air pressure is 2～6 * 10
-2Pa.
2, high photoconductive gain carbon nitride films preparation method according to claim 1 is characterized in that concrete steps are as follows:
1. substrate cleans; 2. settle substrate; 3. vacuumize and distribution; 4. open the Kaufman ion source; 5. cvd nitride carbon film; 6. photoconductive gain test.
3, high photoconductive gain carbon nitride films preparation method according to claim 1 and 2, its feature are that also substrate cleans specific as follows:
The surface of adopting semi-conductor cleaning of the conventional end to carry out substrate is just cleaned, and substrate is placed on uses ultrasonic cleaning in the deionized water again, and with the ionized water flushing for several times, nitrogen dries up.
4, high photoconductive gain carbon nitride films preparation method according to claim 1 and 2, its feature also are, settle substrate specific as follows:
The target body of target, Kaufman ion beam source, and film substrate form certain relative position, the target surface of target body becomes 45 to spend constant cant angle with horizontal plane, film substrate becomes the θ angle with the weight line; Adopt the high energy nitrogen ion beam to plunder the surface of penetrating the bombardment film, with the carbon nitride films of carbon ion reaction with the acquisition high nitrogen-containing, grazing angle is the θ angle, the span at θ angle is 0 degree～20 degree, target body is constantly cooled off by recirculated water, film substrate is perhaps utilized in heavy membrane process the temperature that film substrate raises because of the ionic bombardment by heater heats to 100 ℃～500 ℃.
5, high photoconductive gain carbon nitride films preparation method according to claim 1 and 2, its feature also is, vacuumizes with distribution specific as follows:
Adopt mechanical pump to take out rough vacuum, diffusion pump pumping high vacuum, base vacuum finally reach 1 * 10
-4Pa pressure, by the input flow rate of mass flowmeter and noticeable degree nitrogen, the pressure of control reaction chamber is 2 * 10
-2～6 * 10
-2Pa.
6, high photoconductive gain carbon nitride films preparation method according to claim 1 and 2, its feature are that also it is specific as follows to open the Kaufman ion source:
The Kaufman ion beam source generates ionic fluid in vacuum chamber, the Kaufman ion source can generate ionic current and speeding-up ion stream directive target body, high-octane ion directly bombards target body, the target body material is hit with ion, atom or atomic group form, this kind particulate splashes on the matrix of side with high-energy once more, is deposited on the surface of matrix; Adopting high purity graphite is the target body material, and high-purity nitrogen is the working gas and the sputter gas of ion beam source; Nitrogen is sent in the ion source through vacuum pipe by gas meter, and the nitrogen ion beam of Chan Shenging is both as reactive ion beam, again as the plasma sputter bundle here.
7, high photoconductive gain carbon nitride films preparation method according to claim 6, its feature also is, adopt one or two Kaufman ion beam source, when adopting a Kaufman ion beam source, then this Kaufman ion beam source is a kind of divergence form ion source, the ionic fluid that it produced is both as reactive ion beam, for the generation of carbon nitride films provides the nitrogen ion of participating in reaction, again as the plasma sputter bundle; When adopting two Kaufman ion beam sources, then one provides the plasma sputter bundle, and another provides the required reactive ion beam of generation of carbon nitride films.
8, high photoconductive gain carbon nitride films preparation method according to claim 1 and 2, its feature is that also cvd nitride carbon film is specific as follows:
Kaufman ion source ion beam intensity of flow is 30～80mA/cm
2Between regulate, the beam energy of ionic fluid is that 300～800eV regulates, the line stability is ± 1.0%/h, acceleration voltage changes in 100V～500V, depositing time is 1～3 hour.
9, high photoconductive gain carbon nitride films preparation method according to claim 1 and 2, its feature are that also the photoconductive gain test is specific as follows:
Sedimentary film is carried out the photoconduction test, and the dark conductance of the source table MEASUREMENTS OF THIN of employing Keithley company and the electricity of illumination are led, and calculate photoconductive gain with following formula then: (electricity of illumination is led-dark conductance)/dark conductance.
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|---|---|---|---|
| CN 03116464 CN1265018C (en) | 2003-04-17 | 2003-04-17 | Method for preparing high photoconductive gain carbon nitride film |
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| CN 03116464 CN1265018C (en) | 2003-04-17 | 2003-04-17 | Method for preparing high photoconductive gain carbon nitride film |
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| CN1265018C CN1265018C (en) | 2006-07-19 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534528A (en) * | 2010-12-31 | 2012-07-04 | 鸿富锦精密工业（深圳）有限公司 | Film coating part and preparation method thereof |
| CN106835017A (en) * | 2017-02-17 | 2017-06-13 | 北京埃德万斯离子束技术研究所股份有限公司 | Ion beam reactive sputtering depositing device and aluminum nitride thin membrane preparation method based on Nitrogen ion source |
| CN107475668A (en) * | 2017-09-07 | 2017-12-15 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of high resistivity CN films |
| CN107653438A (en) * | 2017-09-25 | 2018-02-02 | 中国科学院兰州化学物理研究所 | A kind of preparation method with the long-acting greasy property C film of vacuum |
| CN110783049A (en) * | 2019-10-25 | 2020-02-11 | 北京朝歌汉荣科技有限公司 | Preparation method of tantalum nitride film |
| CN114774846A (en) * | 2022-04-14 | 2022-07-22 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of N-doped C film |
-
2003
- 2003-04-17 CN CN 03116464 patent/CN1265018C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534528A (en) * | 2010-12-31 | 2012-07-04 | 鸿富锦精密工业（深圳）有限公司 | Film coating part and preparation method thereof |
| CN106835017A (en) * | 2017-02-17 | 2017-06-13 | 北京埃德万斯离子束技术研究所股份有限公司 | Ion beam reactive sputtering depositing device and aluminum nitride thin membrane preparation method based on Nitrogen ion source |
| CN106835017B (en) * | 2017-02-17 | 2019-11-05 | 北京埃德万斯离子束技术研究所股份有限公司 | Ion beam reactive sputtering depositing device and aluminum nitride thin membrane preparation method based on Nitrogen ion source |
| CN107475668A (en) * | 2017-09-07 | 2017-12-15 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of high resistivity CN films |
| CN107653438A (en) * | 2017-09-25 | 2018-02-02 | 中国科学院兰州化学物理研究所 | A kind of preparation method with the long-acting greasy property C film of vacuum |
| CN110783049A (en) * | 2019-10-25 | 2020-02-11 | 北京朝歌汉荣科技有限公司 | Preparation method of tantalum nitride film |
| CN114774846A (en) * | 2022-04-14 | 2022-07-22 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of N-doped C film |
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| CN1265018C (en) | 2006-07-19 |
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