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WO2000055895A1 - Method of forming an aluminum oxide film - Google Patents

Method of forming an aluminum oxide film

Info

Publication number
WO2000055895A1
WO2000055895A1 PCT/KR2000/000204 KR0000204W WO2000055895A1 WO 2000055895 A1 WO2000055895 A1 WO 2000055895A1 KR 0000204 W KR0000204 W KR 0000204W WO 2000055895 A1 WO2000055895 A1 WO 2000055895A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
film
aluminum
oxide
method
gas
Prior art date
Application number
PCT/KR2000/000204
Other languages
French (fr)
Inventor
Won-Yong Koh
Original Assignee
Genitech, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

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Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02178Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02225Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/314Inorganic layers
    • H01L21/316Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31604Deposition from a gas or vapour
    • H01L21/31616Deposition of Al2O3

Abstract

The present invention relates to a method of forming an aluminum oxide film for use in semiconductor devices on a substrate. Organo-aluminum compound and alcohol, which are sources for the aluminum oxide film formation, are first prepared as gas phases, respectively. Then the gas phase sources are sequentially applied to the substrate to form an aluminum oxide film. In general, alcohol can be evacuated faster than water vapor in a vacuum chamber, which significantly reduces time required for source supply cycle. Therefore, according to the present invention, the growth rate of the aluminum oxide filmn can be increased compared with prior art methods. In addition, the cost associated with semiconductor device fabrication can be reduced because the temperature of both gas supply unit and a reactor can be decreased.

Description

METHOD OF FORMING AN ALUMINUM OXIDE FILM

TECHNICAL FIELD

The present invention relates to a method of forming an aluminum oxide film, and more particularly to a method of forming an aluminum oxide film on a substrate for semiconductor devices.

BACKGROUND ART

Aluminum oxide film is well known to be used widely not only for optical purposes but also for protection films, gate oxide films and optical lithography masks for semiconductor devices as shown in the reference 1. (reference 1 : E. Fredriksson and J.O. Carlsson, Journal of Chemical Vapor Deposition, vol. 1, p. 333 (1993)) Furthermore, reference 2 reported the use of aluminum oxide film for protection from hydrogen diffusion by forming an ultra-thin aluminum oxide film on a PZT(PbZrTiO3) dielectric layer of a FeRAM(Ferroelectric Random Access Memory) (reference 2: Sang Min Lee, Young Kwan Park, In Son Park, Chang Soo Park, Cha Young Ryu, Sang In Lee, Mun Yong Lee, Abstract of the 5th Korean Semiconductor Society p. 255 (1998)).

Compared to the conventional chemical vapor deposition method which provides source materials of a thin film simultaneously, the sequential supply of source materials on a substrate can form a thin film only by a chemical reaction on a substrate surface. Therefore, the latter method can grow a thin film of uniform thickness irrespective of uneven substrate surface, and can control precisely film thickness because the growth of film depends not on process time but on the number of source material supply cycles. It is well described in the "Atomic Layer Epitaxy" edited by T. Suntola and M. Simpson (reference 3: T. Suntola and M. Simpson eds. Atomic Layer Epitaxy, Blackie, London (1990)).

As an application of the latter method, the formation of aluminum oxide film having a uniform thickness on an uneven substrate surface by a sequential supply of trimethylaluminum and water vapor was proposed in the reference 4. (reference 4: Y. Kim, S. M. Lee, C. S. Park, S. I. Lee, and M. Y. Lee, Applied Physics Letters, vol. 71, p. 3604 (1997)). Referring to the reference 4, trimethylaluminum, argon, water vapor and argon are sequentially supplied for 1, 14, 1, and 14 seconds, respectively in each cycle while keeping the substrate at a temperature of 370°C in a reactor heated at 150°C. In each source material supply cycle, the film grows by 0.19nm which makes the total film growth rate of 0.38nm/min. This growth rate is too slow to be applied to semiconductor device fabrication. In order to enhance the film growth rate, each source material supply cycle should be shortened. In the technology disclosed in the reference 4, water vapor is used in the film growth. However, the water vapor is difficult to evacuate in a vacuum chamber, which makes the decrease of material supply cycle time difficult. Furthermore, in case of using water vapor for the formation of an aluminum oxide film, the reactor and the gas supply unit where the water vapor passes should be kept at high temperature because water vapor is easily condensed in a cold unit. It increases energy consumption and workers may get burned during the operation and maintenance of the equipment.

DISCLOSURE OF INVENTION Accordingly, it is an object of the present invention to provide a method of forming an aluminum oxide film by employing source materials which can be easily evacuated in a vacuum chamber and are less susceptible to condense in a reactor. It is another object of the present invention is to provide a method which can form an aluminum oxide film faster than the method which employs water vapor.

In order to achieve the above objects, the method of forming an aluminum oxide film of the present invention comprises the steps of: preparing gases of organo-aluminum compound and alcohol for forming an aluminum oxide film; and contacting said gases sequentially and repeatedly onto a substrate.

The number of carbons in the alcohol molecule is preferably from 2 to 6, and more preferably the alcohol is isopropanol which is widely used in the semiconductor device fabrication.

Furthermore, the organo-aluminum compound is preferably trialkylaluminum, and more preferably the trialkylaluminum is trimethylaluminum.

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiment of the present invention will be described below.

First of all, trimethylaluminum and isopropanol are gasified and are supplied into a deposition chamber. Argon gas is provided as a purge gas between the supplies of the gasified trimethylaluminum and isopropanol. Because isopropanol has a high vapor pressure, it is supplied into the reactor directly using a carrier gas without an additional heating process. Trimethylaluminum gas, argon purge gas, isopropanol gas and argon purge gas are sequentially supplied for 2, 2, 2 and 2 seconds, respectively in each cycle which makes the gas supply period of 8 seconds. The trimethylaluminum decomposes above 300°C, so the source materials must be supplied at a temperature lower than 300°C to grow a film only by a surface reaction. When the film is grown on a substrate kept at 250 ~ 290 °C, the film growth rate by measuring the film thickness using an ellipsometer is determined to be 0.08nm per source material supply cycle or 0.60nm/min.

INDUSTRIAL APPLICABILITY

According to this invention, the temperature for gas supply unit and a reactor can be lowered compared to the previous methods. It can, therefore, simplify apparatus necessary for fabricating semiconductor devices and lower manufacturing cost. Furthermore, an aluminum oxide film with superior step coverage can be grown faster than prior art methods.

Claims

WHAT IS CLAIMED IS :
1. A method of forming an aluminum oxide film comprising the steps of: preparing gases of organo-aluminum compound and alcohol for forming an aluminum oxide film; and contacting said gases sequentially and repeatedly onto a substrate.
2. The method according to claim 1 , wherein the number of carbons in said alcohol molecule is from 2 to 6.
3. The method according to claim 2, wherein said alcohol is isopropanol.
4. The method according to any of claims 1 to 3, wherein said orgoano-aluminum compound is trialkylaluminum.
5. The method according to claim 4, wherein said trialkylaluminum is trimethylaluminum.
6. The method according to claim 1, wherein the temperature of substrate is kept at 250 ~- 290°C at the step of contacting said gases sequentially and repeatedly onto a substrate.
PCT/KR2000/000204 1999-03-16 2000-03-14 Method of forming an aluminum oxide film WO2000055895A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR19990008740A KR20000060438A (en) 1999-03-16 1999-03-16 Method for forming aluminum oxide films
KR1999/8740 1999-03-16

Publications (1)

Publication Number Publication Date
WO2000055895A1 true true WO2000055895A1 (en) 2000-09-21

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2000/000204 WO2000055895A1 (en) 1999-03-16 2000-03-14 Method of forming an aluminum oxide film

Country Status (2)

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KR (1) KR20000060438A (en)
WO (1) WO2000055895A1 (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002031875A2 (en) * 2000-10-10 2002-04-18 Asm America, Inc. Dielectric interface films and methods therefor
WO2004002154A2 (en) 2002-06-25 2003-12-31 Televes, S.A. System for the reception, processing, and distribution of signals
US6727169B1 (en) 1999-10-15 2004-04-27 Asm International, N.V. Method of making conformal lining layers for damascene metallization
US6743475B2 (en) 2000-10-23 2004-06-01 Asm International N.V. Process for producing aluminum oxide films at low temperatures
US6811814B2 (en) 2001-01-16 2004-11-02 Applied Materials, Inc. Method for growing thin films by catalytic enhancement
US6902763B1 (en) 1999-10-15 2005-06-07 Asm International N.V. Method for depositing nanolaminate thin films on sensitive surfaces
US7438760B2 (en) 2005-02-04 2008-10-21 Asm America, Inc. Methods of making substitutionally carbon-doped crystalline Si-containing materials by chemical vapor deposition
US7476420B2 (en) 2000-10-23 2009-01-13 Asm International N.V. Process for producing metal oxide films at low temperatures
US7608549B2 (en) 2005-03-15 2009-10-27 Asm America, Inc. Method of forming non-conformal layers
US7749871B2 (en) 1999-10-15 2010-07-06 Asm International N.V. Method for depositing nanolaminate thin films on sensitive surfaces
US8841182B1 (en) 2013-03-14 2014-09-23 Asm Ip Holding B.V. Silane and borane treatments for titanium carbide films
US8846550B1 (en) 2013-03-14 2014-09-30 Asm Ip Holding B.V. Silane or borane treatment of metal thin films
US8921205B2 (en) 2002-08-14 2014-12-30 Asm America, Inc. Deposition of amorphous silicon-containing films
US8993055B2 (en) 2005-10-27 2015-03-31 Asm International N.V. Enhanced thin film deposition
US9312131B2 (en) 2006-06-07 2016-04-12 Asm America, Inc. Selective epitaxial formation of semiconductive films
US9394609B2 (en) 2014-02-13 2016-07-19 Asm Ip Holding B.V. Atomic layer deposition of aluminum fluoride thin films
US9631272B2 (en) 2008-04-16 2017-04-25 Asm America, Inc. Atomic layer deposition of metal carbide films using aluminum hydrocarbon compounds
US9704716B2 (en) 2013-03-13 2017-07-11 Asm Ip Holding B.V. Deposition of smooth metal nitride films
US9786491B2 (en) 2015-11-12 2017-10-10 Asm Ip Holding B.V. Formation of SiOCN thin films
US9786492B2 (en) 2015-11-12 2017-10-10 Asm Ip Holding B.V. Formation of SiOCN thin films
US9941425B2 (en) 2015-10-16 2018-04-10 Asm Ip Holdings B.V. Photoactive devices and materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
APPLIED PHYSICS LETTERS, vol. 71, 1997, pages 3604 *

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6902763B1 (en) 1999-10-15 2005-06-07 Asm International N.V. Method for depositing nanolaminate thin films on sensitive surfaces
US7749871B2 (en) 1999-10-15 2010-07-06 Asm International N.V. Method for depositing nanolaminate thin films on sensitive surfaces
US6727169B1 (en) 1999-10-15 2004-04-27 Asm International, N.V. Method of making conformal lining layers for damascene metallization
US7102235B2 (en) 1999-10-15 2006-09-05 Asm International N.V. Conformal lining layers for damascene metallization
WO2002031875A3 (en) * 2000-10-10 2003-01-09 Asm Inc Dielectric interface films and methods therefor
US6660660B2 (en) 2000-10-10 2003-12-09 Asm International, Nv. Methods for making a dielectric stack in an integrated circuit
US7038284B2 (en) 2000-10-10 2006-05-02 Asm International, N.V. Methods for making a dielectric stack in an integrated circuit
WO2002031875A2 (en) * 2000-10-10 2002-04-18 Asm America, Inc. Dielectric interface films and methods therefor
US6884465B2 (en) 2000-10-23 2005-04-26 Asm International Nv Process for producing aluminum oxide films at low temperatures
US6743475B2 (en) 2000-10-23 2004-06-01 Asm International N.V. Process for producing aluminum oxide films at low temperatures
US7476420B2 (en) 2000-10-23 2009-01-13 Asm International N.V. Process for producing metal oxide films at low temperatures
US6811814B2 (en) 2001-01-16 2004-11-02 Applied Materials, Inc. Method for growing thin films by catalytic enhancement
WO2004002154A2 (en) 2002-06-25 2003-12-31 Televes, S.A. System for the reception, processing, and distribution of signals
US8921205B2 (en) 2002-08-14 2014-12-30 Asm America, Inc. Deposition of amorphous silicon-containing films
US7438760B2 (en) 2005-02-04 2008-10-21 Asm America, Inc. Methods of making substitutionally carbon-doped crystalline Si-containing materials by chemical vapor deposition
US9190515B2 (en) 2005-02-04 2015-11-17 Asm America, Inc. Structure comprises an As-deposited doped single crystalline Si-containing film
US7608549B2 (en) 2005-03-15 2009-10-27 Asm America, Inc. Method of forming non-conformal layers
US9831094B2 (en) 2005-10-27 2017-11-28 Asm International N.V. Enhanced thin film deposition
US8993055B2 (en) 2005-10-27 2015-03-31 Asm International N.V. Enhanced thin film deposition
US9127351B2 (en) 2005-10-27 2015-09-08 Asm International N.V. Enhanced thin film deposition
US9312131B2 (en) 2006-06-07 2016-04-12 Asm America, Inc. Selective epitaxial formation of semiconductive films
US9631272B2 (en) 2008-04-16 2017-04-25 Asm America, Inc. Atomic layer deposition of metal carbide films using aluminum hydrocarbon compounds
US9704716B2 (en) 2013-03-13 2017-07-11 Asm Ip Holding B.V. Deposition of smooth metal nitride films
US8846550B1 (en) 2013-03-14 2014-09-30 Asm Ip Holding B.V. Silane or borane treatment of metal thin films
US9236247B2 (en) 2013-03-14 2016-01-12 Asm Ip Holding B.V. Silane and borane treatments for titanium carbide films
US9583348B2 (en) 2013-03-14 2017-02-28 Asm Ip Holding B.V. Silane and borane treatments for titanium carbide films
US9111749B2 (en) 2013-03-14 2015-08-18 Asm Ip Holdings B.V. Silane or borane treatment of metal thin films
US8841182B1 (en) 2013-03-14 2014-09-23 Asm Ip Holding B.V. Silane and borane treatments for titanium carbide films
US9394609B2 (en) 2014-02-13 2016-07-19 Asm Ip Holding B.V. Atomic layer deposition of aluminum fluoride thin films
US9941425B2 (en) 2015-10-16 2018-04-10 Asm Ip Holdings B.V. Photoactive devices and materials
US9786491B2 (en) 2015-11-12 2017-10-10 Asm Ip Holding B.V. Formation of SiOCN thin films
US9786492B2 (en) 2015-11-12 2017-10-10 Asm Ip Holding B.V. Formation of SiOCN thin films

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