CN1032768C - Low temp. deposition fine-particle diamond film by microwave method - Google Patents
Low temp. deposition fine-particle diamond film by microwave method Download PDFInfo
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- CN1032768C CN1032768C CN 91102584 CN91102584A CN1032768C CN 1032768 C CN1032768 C CN 1032768C CN 91102584 CN91102584 CN 91102584 CN 91102584 A CN91102584 A CN 91102584A CN 1032768 C CN1032768 C CN 1032768C
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Abstract
The present invention provides a technology for depositing diamond films which can be applied to an optical field and an electrical field through a chemical vapor deposition technology. The present invention is characterized in that working gases contain 0.1 to 10% of high purity oxygen, 0.1 to 10% of high purity methane, and high purity hydrogen as the rest. The pressure of the working gases is from 1 to 100 taus, and the microwave power is from 100 to 500 w in the process of deposition of the diamond films. The present invention has the advantages of simple technology and good repeatability. Besides, the present invention breaks through the application field of the diamond films, and can be applied to the optical field and the electrical field.
Description
The invention belongs to chemical vapour deposition and process deposits, can be used for the technology of the diamond thin of optical field.
At present.Various deposition of diamond thin films technology has been invented by domestic and international different research unit, comprises with microwave plasma generation equipment in comparatively high temps deposit diamond film technology (Japanese Sumitomo electrical equipment house journal: EP-376694) and with pulse laser method (International Business Machine Corporation (IBM) patent EP-382341) or electron beam heating or evaporation ionization (International Business Machine Corporation (IBM) patent EP-360994 and the patent US4961958 of California, USA university) graphite target and the technology of low temperature depositing diamond film.This two classes technology and the present invention have tangible difference, and last class processing requirement substrate temperature maintains 650-1200 ℃ in deposition process, thereby have limited its application possibility at some electricity fields (as the thermodiffusion film of integrated circuit (IC) chip).Though back one class technology can be at the low temperature deposit film that reaches about 100 ℃, but its document fails to prove that the film of its production possesses crystal characteristic, and its detection means (comprising TEM diffraction and Raman reflection primary spectrum) only can prove a kind of amorphous or crystallite film that possesses diamond lattic structure.And adopt this technology under Huas microscope or scanning electron microscope, to observe directly diamond crystal.
The object of the present invention is to provide a kind of new processing method.The advantage that possesses aforementioned two class methods simultaneously, and can overcome the two defective.In temperature is that 200-600 ℃ scope deposits and has tiny even poly grains (about 0.3um-2um), and surface smoothness is diamond thin preferably.
Ultimate principle of the present invention is, utilize microwave plasma generation device in the silica tube of frequency for the microwave intervening acts working spaces of 2.45GHz, the mixed gas of hydrogen, methane and the oxygen of specified proportion decomposites hydrogen and Sauerstoffatom and various carbonaceous ion and atomic group in the ionization tube under 1-100t low pressure.Produce diamond in the substrate surface deposition, the molecular grouping of amorphous carbon and graphite, hydrogen in the gas and Sauerstoffatom etc. produce selective etching to graphite and amorphous carbon, and finally making and obtaining diamond lattic structure on the substrate is main crystalline structure.The crystal grain forming core and even to a certain degree promptly becoming one deck size, the fine and close polycrystalline rete of growing up.
The pre-treatment of substrate; The substrate (as＜111〉silicon single crystal) of polishing is ground (craft or ultrasonic wave) with the diamond powder of 0.5-5um, clean the back and carry out ultrasonic cleaning with acetone and anhydrous methanol;
The deposition of film: clean substrate is placed in the silica tube, be evacuated to 3-1 * 10
-2T selects ratio (hydrogen: methane: oxygen flow ratio=99.8-80: 0.1-10: 0.1-10, unit are per minute standard liter) the general work gas of hydrogen, methane and oxygen to contain the high purity oxygen gas of 0.1-10% as requested.The preferential 2-8% that selects, the high-purity methane of 0.1-19% preferentially is chosen as 5-10%, and surplus is that hydrogen fills in the working spaces, open microwave high pressure power supply input microwave power then, its value is also selected between 100-500W according to the temperature and the substrate position of required deposition substrate.This moment, film promptly began growth.This technology also take to change substrate in plasma body and below the position, the measure that substrate temperature is obviously reduced can be in from exciting the plasma center to leaving the position of plasma body lower surface weight apart from 3cm substrate.
The control of thickness: from 600-200 ℃ depositing temperature, the speed of film thickness growth changed from 0.5um/ hour to 0.005um/ hour, determined that according to the variation range of prediction depositing time is to obtain the film of pre-determined thickness.Can take out substrate after deposition finishes tests.
Technology of the present invention is simple, process repeatability is strong, can on unlike material, (comprise silicon, quartz, molybdenum etc.) again and deposit the well thin diamond film of crystalline form, and depositing temperature is lower, be not damaged in a organized way with inner former in the surface of some substrate, therefore can break through the Application Areas of diamond thin, make this kind film use optics (comprising infrared optics, X-ray and laser) field and electricity (the direct deposition that comprises the heat dissipation of integrated circuit chip film) field and develop new purposes.
Embodiment
(1) 40 minutes 20 * 20m of diamond powder ultrasonic wave polishing of usefulness 5um
2The polishing of thick 0.5mm＜111〉monocrystalline silicon piece, through cleaning, feed 60SccM (per minute standard liter, (down together) hydrogen, 3SccM methane and 1.2SccM oxygen after finding time, substrate is positioned at the plasma body central section, microwave power is 500W, is 580 ℃ after substrate temperature is calibrated, and depositing time is 24 hours.Result to this film scanning electron microscopic observation shows it is that one deck is evenly fine and close, particle size is about 1.5um, based on＜111〉the polycrystalline diamond film of the trilateral (spatial form is a regular octahedron) of face, also prove the diamond film that has obtained having the good crystalline feature with Raman scattering and X-ray diffraction method.And at 200cm
-1～1000cm
-1Wave-number range observe the infrared anti-reflection effect of diamond film to silicon substrate.
(2) substrate is identical with (1), but grind with the 0.5um bortz powder, after finding time, cleaning feeds 100SccM hydrogen, 5SccM methane and 3SccM oxygen, operating pressure is 10 τ, substrate is positioned at plasma body bottom half (apart from lower surface 1cm), microwave power is 150W, substrate temperature is 410 ℃, depositing time is 90 hours, and the film that obtains thus is even compact still, and particle size is 0.5-1um, based on (111) face, also prove that with Raman and X-ray diffraction method film has tangible crystal characteristic.
Claims (2)
- One kind at low temperatures on silicon substrate the deposition polycrystalline diamond films method, wherein adopt microwave plasma CVD (MWCVD) technology, employing feeds high purity oxygen in the mixed atmosphere of methane and hydrogen, and the step of suitably adjusting the relative distance of microwave power and substrate and microwave plasma ball, the diamond thin of deposition small grains (0.2-2um) when the substrate surface actual temperature is 200-600 ℃, process parameters range is: contain oxygen 0.1-10% in the atmosphere, methane 0.1-10%, surplus is a hydrogen.Pressure is 1-100Torr during deposition, and microwave power is 100-500 watt, and substrate is positioned at from microwave plasma ball center to leaving plasma ball lower surface 3cm.
- 2. the method for diamond films at low temperatures according to claim 1 is characterized in that the preferential working range of selecting is; Pressure 1-20Torr, methane content 5-10%, oxygen content 2-8%, surplus is a hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91102584 CN1032768C (en) | 1991-04-28 | 1991-04-28 | Low temp. deposition fine-particle diamond film by microwave method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91102584 CN1032768C (en) | 1991-04-28 | 1991-04-28 | Low temp. deposition fine-particle diamond film by microwave method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1066299A CN1066299A (en) | 1992-11-18 |
| CN1032768C true CN1032768C (en) | 1996-09-11 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91102584 Expired - Fee Related CN1032768C (en) | 1991-04-28 | 1991-04-28 | Low temp. deposition fine-particle diamond film by microwave method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1032768C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005103326A1 (en) * | 2004-04-19 | 2005-11-03 | National Institute Of Advanced Industrial Science And Technology | Carbon film |
-
1991
- 1991-04-28 CN CN 91102584 patent/CN1032768C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1066299A (en) | 1992-11-18 |
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