CN102560419A - Method for preparing alumina ultrathin film - Google Patents
Method for preparing alumina ultrathin film Download PDFInfo
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- CN102560419A CN102560419A CN2011103869231A CN201110386923A CN102560419A CN 102560419 A CN102560419 A CN 102560419A CN 2011103869231 A CN2011103869231 A CN 2011103869231A CN 201110386923 A CN201110386923 A CN 201110386923A CN 102560419 A CN102560419 A CN 102560419A
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Abstract
The invention discloses a method for preparing an alumina ultrathin film, which is used for preparing an alumina ultrathin film material by sequentially feeding in a pulse mode and utilizing a self-limiting adsorption effect. The method for preparing the alumina ultrathin film is realized on the basis of an atomic layer deposition system, and has the advantages of simple growth condition, high repeatability, no impurities, high controllability and the like. The alumina ultra-thin film prepared by the method has wide application ranges in the fields of semiconductors, integrated ferroelectrics, optical coating, solar cells and the like.
Description
Technical field
The present invention relates to a kind of preparation method of thin-film material, specifically a kind of at room temperature based on the method for technique for atomic layer deposition growth aluminum oxide ultrathin film.
Technical background
Aluminum oxide film is because of having good physical and chemical performance; Like physical strength and hardness height, Heat stability is good, broad stopband, light transmission rate is high, insulativity is splendid etc.; Have a wide range of applications in many fields such as machinery, optics and microelectronics, therefore significant to the research of aluminum oxide film.At microelectronic, along with the integrated level of si-substrate integrated circuit improves constantly, can't ignore because of tunnelling current under nanoscale as the earth silicon material of field effect transistor gate material, more and more be not suitable for as insulating material.Aluminum oxide film has caused researchist's interest as the equivalent material of silicon-dioxide.Technique for atomic layer deposition is particularly suitable for the growth of ultrathin film owing to have advantages such as film growth thickness is accurately controlled, step coverage is splendid, uses more and more wider at microelectronic.The photopermeability of aluminum oxide film Yin Qigao can also be used for the light collection layer of solar cell.Utilization technique for atomic layer deposition growth aluminum oxide more research has been arranged, but mostly the presoma that adopts at present is trimethylaluminium and water, and suitable growth temperature is between 200～400 ℃.The low-gap semiconductor material of, highly volatile low for fusing points such as Te-Cd-Hgs need be grown alumina insulating layer above that when making device such as infrared eye, and traditional atom layer deposition process is because temperature is higher relatively and no longer suitable; In addition; Grow aluminum oxide with preparation new type integrated circuit, display device on some flexible organic film surfaces (like pvdf, polyimide etc.); Therefore existing technique for atomic layer deposition is too high also no longer suitable because of its temperature equally, presses for the growth technique of searching aluminum oxide film under low temperature more.Though research is arranged (referring to paper: Chem. Mater. 2004; 16; 639-645) show to adopt and use water as the oxygen presoma and also can realize ald below 100 ℃; But the very long rare gas element flush time of its arts demand makes that to realize the monolayer adsorption of water molecules its time loss in practicality is of a specified duration excessively, is unfavorable for enhancing productivity; And the hydrogen foreign matter content is higher in the film that obtains, and is difficult to further improve material physical property.
Summary of the invention
A kind of growth temperature that the objective of the invention is to be directed against the deficiency of prior art and provide is reduced to the aluminum oxide ultrathin film preparation methods of room temperature, and one side makes that the growth alumina insulating layer becomes possibility on the low-gap semiconductor material of highly volatile under the high temperature such as Te-Cd-Hg and flexible organic film material; Secondly also making no longer needs any heat-processed in the material process of growth, has greatly reduced the energy consumption in the manufacturing processed; And possesses the compatibility with existing silicon-based semiconductor technology.
For realizing the foregoing invention purpose, the concrete technical scheme of the present invention is:
A kind of preparation method of aluminum oxide ultrathin film specifically is meant and a kind ofly enters the source successively, utilizes the method that is prepared into the aluminum oxide ultrathin membrane from the limiting surface adsorption effect based on pulse mode.
Comprise following concrete steps:
⑴, raw material
Trimethylaluminium, nitrogen or argon gas, oxygen and substrate; Nitrogen or argon gas and oxygen employing purity are 99.9999% gas; Substrate is silicon chip, lanthanum nickelate thin film, indium oxide film or platinized platinum;
⑵, preparation aluminum oxide ultrathin film
Substrate with after the absolute ethyl alcohol flushing, is dried up with nitrogen, be positioned on the sample tray, send into the vacuum reaction chamber of atomic layer deposition system, vacuumize and make vacuum tightness reach 1～3hpa;
The substrate that is fixed on the sample tray of vacuum reaction chamber keeps at room temperature; The source bottle that trimethylaluminium is housed freezed makes its temperature remain on 15～20 ℃, and oxygen and nitrogen produce ozone gas through ozonizer after mixing according to 95: 5 volume ratio; Feed nitrogen or argon gas in the depositing system, make the interior intermediate space air pressure that reaches of reaction chamber remain on 1～3hpa and 6～15hpa respectively; Each growth circulation is made up of following four gas pulses:
A, trimethylaluminium pulse 0.1 second use nitrogen or argon gas to be transported to reaction chamber as carrier gas, and carrier gas flux is 150sccm;
B, nitrogen or argon cleaning cavity 2～30 seconds, flow is 150sccm;
C, ozone pulse 3 seconds, ozone flow are 200～300sccm, use nitrogen or argon gas to be transported to reaction chamber as carrier gas, and carrier gas flux is 150sccm;
D, nitrogen or argon cleaning cavity 6 seconds, flow is 150sccm;
Utilization makes the aluminum oxide ultrathin film from the limiting surface adsorption effect; When cycle index 250 the time, the film thickness that obtains is 35.33 nanometers; When cycle index 500 the time, about 70 nanometers of the film thickness that obtains.
Above-mentioned reaction is in the vacuum reaction chamber of sealing, to carry out.This preparation method realizes based on atomic layer deposition system.
What the present invention prepared is a kind of aluminum oxide ultrathin film material; The aluminum oxide film that obtains with respect to other atom layer deposition process; Excellent insulation performance, film surface densification are smooth except possessing equally for this material, growth thickness accurate controlled, step coverage is splendid, with advantage such as silicon-based semiconductor process compatible; Also possess following characteristics: (1) growth temperature reduces greatly, at room temperature can synthesize.The synthetic aluminum oxide film needed under 200～400 ℃, to obtain in the past, and at room temperature utilized the preparation of ozone synthetic aluminum oxide ultrathin membrane still first; The reduction of growth temperature also causes the very big minimizing of energy consumption in the production process.(2) be particularly suitable for as with the low-gap semiconductor material of highly volatile under the high temperature such as Te-Cd-Hg, semiconductor material that organic film material is the basis and the insulation layer in the device.
Description of drawings
Fig. 1 is the AFM figure of 2000 gained films for cycle index of the present invention, and the right side is an altitude scale;
Fig. 2 is the SEM figure of 2000 gained films for cycle index of the present invention;
Fig. 3 is Al/Al
2O
3The C-V performance chart of the compound MIS structure capacitive of/p-Si device under different frequency, Al wherein
2O
3The growth cycle index is 2000 times, and Al electrodes use vacuum vapor deposition method is at Al
2O
3The surface makes and obtains;
Fig. 4 is Al/Al
2O
3The I-V graphic representation of the compound MIS structure capacitive of/Pt device, Al wherein
2O
3The growth cycle index is 1000 times, and Al electrodes use vacuum vapor deposition method is at Al
2O
3The surface makes and obtains Al
2O
3The voltage breakdown of ultrathin membrane is 60V nearly, has shown splendid insulating property.
Embodiment
Embodiment 1
After silicon chip substrate used absolute ethyl alcohol flushing, dry up, be positioned on the sample tray, send into the vacuum reaction chamber of atomic layer deposition system, vacuumize and make vacuum tightness reach 3hpa with nitrogen.
The substrate that is fixed on the sample tray of vacuum reaction chamber keeps at room temperature; The source bottle that trimethylaluminium is housed freezed make its temperature remain on 20 ℃; The nitrogen of the oxygen of 99.999% purity and 99.999% purity produces ozone gas through ozonizer after mixing according to 95: 5 volume ratio; Feed rare gas element-nitrogen (purity is 99.9999%) in the depositing system, make in the reaction chamber, intermediate space air pressure remains on 3hpa, 10hpa respectively.
Utilize nitrogen (purity is 99.9999%) as carrier gas, adopt pulse mode to send the vacuum reaction cavity to through pipeline successively two provenances, specifically, the growth of each circulation is made up of following pulse successively:
A, trimethylaluminium pulse 0.1 second use nitrogen or argon gas to be transported to reaction chamber as carrier gas, and carrier gas flux is 150sccm;
B, nitrogen wash cavity 4 seconds, flow are 150sccm;
C, ozone pulse 3 seconds, ozone flow are 300sccm, use nitrogen to be transported to reaction chamber as carrier gas, and carrier gas flux is 150sccm;
D, nitrogen wash cavity 6 seconds, flow are 150sccm.
The limiting growth cycle index is 250 o'clock, and obtaining thickness is the said film sample of 35.33 nanometers.
Embodiment 2
After silicon chip substrate used absolute ethyl alcohol flushing, dry up, be positioned on the sample tray, send into the vacuum reaction chamber of atomic layer deposition system, vacuumize and make vacuum tightness reach 1hpa with nitrogen.
The substrate that is fixed on the sample tray of vacuum reaction chamber keeps at room temperature; The source bottle that trimethylaluminium is housed freezed make its temperature remain on 15 ℃; The nitrogen of the oxygen of 99.999% purity and 99.999% purity produces ozone gas through ozonizer after mixing according to 95: 5 volume ratio.Feed rare gas element-argon gas (purity is 99.9999%) in the depositing system, make in the reaction chamber, intermediate space air pressure remains on 3hpa, 15hpa respectively.
Utilize argon gas (purity is 99.9999%) as carrier gas, adopt pulse mode to send the vacuum reaction cavity to through pipeline successively two provenances, specifically, the growth of each circulation is made up of following pulse successively:
A, trimethylaluminium pulse 0.1 second use argon gas to be transported to reaction chamber as carrier gas, and carrier gas flux is 150sccm;
B, argon cleaning cavity 4 seconds, flow are 150sccm;
C, ozone pulse 3 seconds, ozone flow are 300sccm, use argon gas to be transported to reaction chamber as carrier gas, and carrier gas flux is 150sccm;
D, argon cleaning cavity 6 seconds, flow are 150sccm.
The limiting growth cycle index is 500 o'clock, and obtaining thickness is the said film sample of 70 nanometers.
Claims (1)
1. the preparation method of an aluminum oxide ultrathin film is characterized in that said aluminum oxide ultrathin film is at room temperature to adopt the ald mode to be grown on the substrate and make; Its preparation method comprises following concrete steps:
⑴, raw material
Trimethylaluminium, nitrogen or argon gas, oxygen and substrate; Nitrogen or argon gas and oxygen employing purity are 99.9999% gas; Substrate is silicon chip, lanthanum nickelate thin film, indium oxide film or platinized platinum;
⑵, preparation aluminum oxide ultrathin film
Substrate with after the absolute ethyl alcohol flushing, is dried up with nitrogen, be positioned on the sample tray, send into the vacuum reaction chamber of atomic layer deposition system, vacuumize and make vacuum tightness reach 1～3hpa;
The substrate that is fixed on the sample tray of vacuum reaction chamber keeps at room temperature; The source bottle that trimethylaluminium is housed freezed makes its temperature remain on 15～20 ℃, and oxygen and nitrogen produce ozone gas through ozonizer after mixing according to 95: 5 volume ratio; Feed nitrogen or argon gas in the depositing system, make the interior intermediate space air pressure that reaches of reaction chamber remain on 1～3hpa and 6～15hpa respectively; Each growth circulation is made up of following four gas pulses:
A, trimethylaluminium pulse 0.1 second use nitrogen or argon gas to be transported to reaction chamber as carrier gas, and carrier gas flux is 150sccm;
B, nitrogen or argon cleaning cavity 2～30 seconds, flow is 150sccm;
C, ozone pulse 3 seconds, ozone flow are 200～300sccm, use nitrogen or argon gas to be transported to reaction chamber as carrier gas, and carrier gas flux is 150sccm;
D, nitrogen or argon cleaning cavity 6 seconds, flow is 150sccm;
Utilization makes the aluminum oxide ultrathin film from the limiting surface adsorption effect; When cycle index 250 the time, the film thickness that obtains is 35.33 nanometers; When cycle index 500 the time, about 70 nanometers of the film thickness that obtains.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104698512A (en) * | 2013-12-09 | 2015-06-10 | 东京毅力科创株式会社 | Member with reflection preventing function and manufacturing method thereof |
| CN104862664A (en) * | 2015-05-19 | 2015-08-26 | 南通大学 | Preparation method of ultrathin graphical aluminium oxide film |
| CN105032385A (en) * | 2015-07-08 | 2015-11-11 | 华中科技大学 | Preparation method for metal oxide/platinum nanoparticle composite catalyst |
| CN105355539A (en) * | 2015-10-12 | 2016-02-24 | 华东师范大学 | Preparation method for mercury cadmium telluride surface insulating layer |
| CN108796605A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | A kind of quasi-monocrystalline silicon crucible for casting ingots using aluminum oxide film as barrier layer |
| CN110473888A (en) * | 2019-08-26 | 2019-11-19 | 上海华力集成电路制造有限公司 | The forming method and aluminum oxide film of aluminum oxide film in BSI structure image sensor |
| CN110760818A (en) * | 2019-10-31 | 2020-02-07 | 长春长光圆辰微电子技术有限公司 | Process for growing alumina by using atomic layer deposition technology |
| CN112802734A (en) * | 2020-12-30 | 2021-05-14 | 长春长光圆辰微电子技术有限公司 | Method for depositing single-side film of silicon wafer |
| CN115233188A (en) * | 2022-07-22 | 2022-10-25 | 南京理工大学 | Piece-level Ni-Al 2 O 3 Preparation method of porous energy material |
| CN115583804A (en) * | 2022-10-21 | 2023-01-10 | 湖北大学 | Antireflection super-hydrophobic film, and preparation method and application thereof |
| CN117476441A (en) * | 2023-12-27 | 2024-01-30 | 无锡松煜科技有限公司 | Patterning architecture method for silicon wafer surface |
| CN115233188B (en) * | 2022-07-22 | 2024-05-17 | 南京理工大学 | Sheet grade Ni-Al2O3Preparation method of porous energy material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1619819A (en) * | 2003-11-22 | 2005-05-25 | 海力士半导体有限公司 | Capacitor with hafnium oxide and aluminum oxide alloyed dielectric layer and method for fabricating the same |
| CN101921994A (en) * | 2010-07-30 | 2010-12-22 | 北京印刷学院 | Device and method for depositing ultrathin alumina film by atomic layer |
-
2011
- 2011-11-29 CN CN2011103869231A patent/CN102560419A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1619819A (en) * | 2003-11-22 | 2005-05-25 | 海力士半导体有限公司 | Capacitor with hafnium oxide and aluminum oxide alloyed dielectric layer and method for fabricating the same |
| CN101921994A (en) * | 2010-07-30 | 2010-12-22 | 北京印刷学院 | Device and method for depositing ultrathin alumina film by atomic layer |
Non-Patent Citations (2)
| Title |
|---|
| J.L.VAN HEMMEM ET AL.: "Plasma and Thermal ALD of Al2O3 in a Commercial 200 mm ALD Reactor", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
| 桑利军等: "电子回旋共振等离子体辅助脉冲式沉积氧化铝薄膜的研究", 《真空科学与技术学报》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104698512A (en) * | 2013-12-09 | 2015-06-10 | 东京毅力科创株式会社 | Member with reflection preventing function and manufacturing method thereof |
| CN104698512B (en) * | 2013-12-09 | 2017-09-01 | 东京毅力科创株式会社 | Part and its manufacture method with anti-reflective function |
| CN104862664A (en) * | 2015-05-19 | 2015-08-26 | 南通大学 | Preparation method of ultrathin graphical aluminium oxide film |
| CN105032385A (en) * | 2015-07-08 | 2015-11-11 | 华中科技大学 | Preparation method for metal oxide/platinum nanoparticle composite catalyst |
| CN105032385B (en) * | 2015-07-08 | 2017-09-12 | 华中科技大学 | A kind of preparation method of metal oxide/Pt nanoparticle composite catalyst |
| CN105355539A (en) * | 2015-10-12 | 2016-02-24 | 华东师范大学 | Preparation method for mercury cadmium telluride surface insulating layer |
| CN108796605A (en) * | 2018-06-28 | 2018-11-13 | 浙江大学 | A kind of quasi-monocrystalline silicon crucible for casting ingots using aluminum oxide film as barrier layer |
| CN110473888A (en) * | 2019-08-26 | 2019-11-19 | 上海华力集成电路制造有限公司 | The forming method and aluminum oxide film of aluminum oxide film in BSI structure image sensor |
| CN110760818A (en) * | 2019-10-31 | 2020-02-07 | 长春长光圆辰微电子技术有限公司 | Process for growing alumina by using atomic layer deposition technology |
| CN112802734A (en) * | 2020-12-30 | 2021-05-14 | 长春长光圆辰微电子技术有限公司 | Method for depositing single-side film of silicon wafer |
| CN115233188A (en) * | 2022-07-22 | 2022-10-25 | 南京理工大学 | Piece-level Ni-Al 2 O 3 Preparation method of porous energy material |
| CN115233188B (en) * | 2022-07-22 | 2024-05-17 | 南京理工大学 | Sheet grade Ni-Al2O3Preparation method of porous energy material |
| CN115583804A (en) * | 2022-10-21 | 2023-01-10 | 湖北大学 | Antireflection super-hydrophobic film, and preparation method and application thereof |
| CN117476441A (en) * | 2023-12-27 | 2024-01-30 | 无锡松煜科技有限公司 | Patterning architecture method for silicon wafer surface |
| CN117476441B (en) * | 2023-12-27 | 2024-04-05 | 无锡松煜科技有限公司 | Patterning architecture method for silicon wafer surface |
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Application publication date: 20120711 |