CN100500924C - Method for preparing metal nano-crystal thin film - Google Patents

Method for preparing metal nano-crystal thin film Download PDF

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Publication number
CN100500924C
CN100500924C CNB2006101095625A CN200610109562A CN100500924C CN 100500924 C CN100500924 C CN 100500924C CN B2006101095625 A CNB2006101095625 A CN B2006101095625A CN 200610109562 A CN200610109562 A CN 200610109562A CN 100500924 C CN100500924 C CN 100500924C
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metal nano
thin film
preparation
crystal thin
nano
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CN101122006A (en
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龙世兵
李志刚
刘明
陈宝钦
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Semiconductor Manufacturing International Shanghai Corp
Institute of Microelectronics of CAS
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Institute of Microelectronics of CAS
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Abstract

The invention discloses a method of preparing a metal nano-crystal film, which includes: A. a layer of metal film is deposited on an insulating substrate; B. conductin fast annealing with high temperature in the inert gas, so as to form the separated metal nano-crystal film. The metal nano-crystal film prepared by the invention has very good charge retention and storage characteristics as well as processing compatibility with traditional silicon planes, and is very applicable in preparing high-performance semiconductor memory components. The method of preparing a metal nano-crystal film provided by the invention greatly simplifies the preparing technology, reduces the preparing cost, improves the technological stability and preparing efficiency, and is very good for wide promotion and application of the invention.

Description

A kind of preparation method of metal nano-crystal thin film
Technical field
The present invention relates to nano electron device and technical field of nano-processing, relate in particular to a kind of preparation method of metal nano-crystal thin film.
Background technology
Nanocrystalline material is because median size is small, surface atom is many, specific surface area is big, surface energy is high, thereby its character both had been different from single atom, molecule, be different from common particulate material again, demonstrate characteristics such as unique quantum size effect, surface and interfacial effect, quantum tunneling effect, thereby show and the distinct performance of conventional crystalline material.
This is mainly reflected in aspects such as electric property, optical property, magnetic performance, mechanical property, thermal property, chemical property.In various nanocrystalline materials, silicon nano-crystalline film and part metals nano-crystal film are very suitable for preparing high-performance memory spare.
The metallic nano crystal material of preparation mostly is powder greatly at present, and adopts chemical process synthetic mostly.Application number is that 95112713.6 Chinese invention patent discloses a kind of method that adopts chemical process preparation size controllable nano level silver powder; Application number is that 200410011178.2 Chinese invention patent discloses a kind of gold nanocrystals that adopts the dendrimer protection of the synthetic controllable size of chemical process; Application number is that 200510037955.5 Chinese invention patent discloses a kind of method that adopts chemical process to prepare high density nano metallic film or block materials; Application number is that 03137139.6 Chinese invention patent discloses a kind of method that adopts chemical process to prepare cubes silver nano-crystalline granule film; Application number is that 03121554.8 Chinese invention patent discloses a kind of method that adopts machining process to produce nanocrystalline metal wire rod or band; Application number is that 93111176.5 Chinese invention patent discloses a kind of method that adopts deposition of high melting metal carbonide nanometre crystal by sputtering.
Utilize that method for preparing metallic nano crystal material generally all exists complicated process of preparation, preparation cost height, preparation efficiency is low, material category is single, with the poor compatibility of traditional silicon planner technology, be unfavorable for application in the device preparation.
Summary of the invention
(1) technical problem that will solve
Deficiency at above-mentioned prior art existence, main purpose of the present invention is to provide a kind of preparation method of metal nano-crystal thin film, to simplify preparation technology, reduce preparation cost, to improve preparation efficiency, and the compatibility of raising and traditional silicon planner technology, help application in the device preparation.
(2) technical scheme
For achieving the above object, technical scheme of the present invention is achieved in that
A kind of preparation method of metal nano-crystal thin film, this method comprises:
A, on insulating substrate deposit layer of metal film;
B, in rare gas element high temperature rapid thermal annealing, form the metal nano-crystal thin film that is separated from each other between the nano-crystalline granule, wherein annealing temperature is 700 ℃ to 1600 ℃, annealing time is 5 to 90 seconds.
Insulating substrate described in the steps A is smooth, clean SiO 2, Si 3N 4Or Al 2O 3Insulating substrate.
The method of deposit described in the steps A is sputter or evaporation.
Described sputter comprises magnetron sputtering, radio-frequency sputtering, d.c. sputtering, cosputtering or reactive sputtering, and described evaporation comprises thermal evaporation or electron beam evaporation.
The thickness of metallic film described in the steps A is 2 to 3nm.
Metallic film described in the steps A is elemental metals film or emtal alloy film.
Described elemental metals is Ni, Fe, Co, Mn, Cr, W, Ge, Al, Cu, Au, Ag or Pt, and described metal alloy is NiFe or WTi.
Rare gas element described in the step B is N 2, Ar, He.
(3) beneficial effect
From technique scheme as can be seen, the present invention has following beneficial effect:
1, the metal nano-crystal thin film that utilizes the present invention to prepare has good electric charge capture and storage characteristics, can with traditional silicon planner technology compatibility, be very suitable for being suitable for making high performance semiconductor storage unit.
2, utilize the method for preparing metal nano-crystal thin film provided by the invention, simplified preparation technology greatly, reduced preparation cost, improved technology stability and preparation efficiency, be very beneficial for extensive promotion and application of the present invention.
Description of drawings
Fig. 1 is the realization flow figure of preparation metal nano-crystal thin film overall technological scheme provided by the invention;
Fig. 2 be provided by the invention on insulating substrate the synoptic diagram of depositing metal film;
Fig. 3 carries out the synoptic diagram that high temperature rapid thermal annealing forms metal nano-crystal thin film for provided by the invention to the metals deposited film;
Fig. 4 is the electron scanning micrograph according to the Ni nano-crystal film of first embodiment of the invention preparation;
Fig. 5 is the WSi according to the second embodiment of the invention preparation 2The electron scanning micrograph of nano-crystal film;
Fig. 6 is the electron scanning micrograph according to the WTi nano-crystal film of third embodiment of the invention preparation.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
As shown in Figure 1, Fig. 1 is the realization flow figure of preparation metal nano-crystal thin film overall technological scheme provided by the invention, and this method may further comprise the steps:
Step 101: deposit layer of metal film on insulating substrate.
The technical process corresponding with this step as shown in Figure 2, Fig. 2 be provided by the invention on insulating substrate the synoptic diagram of depositing metal film.Among Fig. 2,1 expression insulating substrate, 2 expression metallic films.
In this step, insulating substrate is smooth, clean SiO 2, Si 3N 4Or Al 2O 3Etc. insulating substrate.The method of deposit is sputter or evaporation, and wherein, sputter comprises magnetron sputtering, radio-frequency sputtering, d.c. sputtering, cosputtering or reactive sputtering etc.; Evaporation comprises thermal evaporation or electron beam evaporation.
The thickness of metallic film is 2 to 3nm.Metallic film can be elemental metals film, metal silicide film or emtal alloy film etc.When metallic film was the elemental metals film, elemental metals was Ni, Fe, Co, Mn, Cr, W, Ge, Al, Cu, Au, Ag or Pt.When metallic film was metal silicide film, metal silicide was WSi 2Or TaSi 2When metallic film was emtal alloy film, metal alloy was NiFe or WTi.
Step 102: high temperature rapid thermal annealing in rare gas element forms isolating metal nano-crystal thin film.
The technical process corresponding with this step as shown in Figure 3, Fig. 3 carries out the synoptic diagram that high temperature rapid thermal annealing forms metal nano-crystal thin film for provided by the invention to the metals deposited film.Among Fig. 3,1 expression insulating substrate, 3 expression metallic nano crystal particles.
In this step, rare gas element can be N 2, Ar or He etc.The temperature of high temperature rapid thermal annealing is generally 700 ℃ to 1600 ℃, and the time of short annealing was generally 5 to 90 seconds.
Realization flow figure based on preparation metal nano-crystal thin film overall technological scheme shown in Figure 1 further describes the method that the present invention prepares metal nano-crystal thin film below in conjunction with specific embodiment.
Embodiment one
Utilize thermooxidizing one deck SiO that on the Si substrate, grows 2Dielectric utilizes magnetron sputtering at SiO then 2The thick Ni metallic film of growth one deck 2 to 3nm on the dielectric is at last at N 2In 800 ℃ of following short annealings 30 seconds, form the Ni nano-crystal film.As shown in Figure 4, Fig. 4 is the electron scanning micrograph according to the Ni nano-crystal film of first embodiment of the invention preparation.Among Fig. 4, Ni nanocrystal diameter is 5 to 20nm, density 3 * 10 11/ cm 2
Embodiment two
Utilize thermooxidizing one deck SiO that on the Si substrate, grows 2Dielectric utilizes magnetron sputtering at SiO then 2The thick WSi of growth one deck 2 to 3nm on the dielectric 2Metallic film is at last at N 2In 1100 ℃ of following short annealings 30 seconds, form WSi 2Nano-crystal film.As shown in Figure 5, Fig. 5 is the WSi according to the second embodiment of the invention preparation 2The electron scanning micrograph of nano-crystal film.Among Fig. 5, WSi 2The nanocrystal diameter is 10 to 30nm, density 1 * 10 11/ cm 2
Embodiment three
Utilize thermooxidizing one deck SiO that on the Si substrate, grows 2Dielectric utilizes magnetron sputtering at SiO then 2The thick WTi metallic film of growth one deck 2 to 3nm on the dielectric is at last at N 2In 800 ℃ of following short annealings 30 seconds, form the WTi nano-crystal film.As shown in Figure 6, Fig. 6 is the electron scanning micrograph according to the WTi nano-crystal film of third embodiment of the invention preparation.Among Fig. 6, WTi nanocrystal diameter is 10 to 40nm, density 1.5 * 10 11/ cm 2
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (8)

1, a kind of preparation method of metal nano-crystal thin film is characterized in that, this method comprises:
A, on insulating substrate deposit layer of metal film;
B, in rare gas element high temperature rapid thermal annealing, form the metal nano-crystal thin film that is separated from each other between the nano-crystalline granule, wherein annealing temperature is 700 ℃ to 1600 ℃, annealing time is 5 to 90 seconds.
2, the preparation method of metal nano-crystal thin film according to claim 1 is characterized in that, insulating substrate described in the steps A is smooth, clean SiO 2, Si 3N 4Or Al 2O 3Insulating substrate.
3, the preparation method of metal nano-crystal thin film according to claim 1 is characterized in that, the method for deposit described in the steps A is sputter or evaporation.
4, the preparation method of metal nano-crystal thin film according to claim 3 is characterized in that, described sputter comprises magnetron sputtering, radio-frequency sputtering, d.c. sputtering, cosputtering or reactive sputtering, and described evaporation comprises thermal evaporation or electron beam evaporation.
5, the preparation method of metal nano-crystal thin film according to claim 1 is characterized in that, the thickness of metallic film described in the steps A is 2 to 3nm.
6, the preparation method of metal nano-crystal thin film according to claim 1 is characterized in that, metallic film described in the steps A is elemental metals film or emtal alloy film.
7, the preparation method of metal nano-crystal thin film according to claim 6 is characterized in that, described elemental metals is Ni, Fe, Co, Mn, Cr, W, Ge, Al, Cu, Au, Ag or Pt, and described metal alloy is NiFe or WTi.
8, the preparation method of metal nano-crystal thin film according to claim 1 is characterized in that, rare gas element described in the step B is N 2, Ar, He.
CNB2006101095625A 2006-08-10 2006-08-10 Method for preparing metal nano-crystal thin film Active CN100500924C (en)

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* Cited by examiner, † Cited by third party
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CN101800242B (en) * 2009-02-11 2013-03-06 中国科学院微电子研究所 Nano electron device using nanocrystal material as Coulomb island and manufacture method thereof
US8652649B2 (en) * 2009-07-10 2014-02-18 Xtalic Corporation Coated articles and methods
CN102244193A (en) * 2010-05-13 2011-11-16 复旦大学 Ruthenium (Ru)-doped tantalum oxide based resistive memory and preparation method thereof
CN102227014A (en) * 2011-03-28 2011-10-26 复旦大学 Resistive random access memory possessing metal nanocrystalline electrode and preparation method thereof
CN102806354A (en) * 2012-07-31 2012-12-05 东南大学 Method for preparing gold nanoparticles by annealing of gold film
CN103074627A (en) * 2013-01-17 2013-05-01 中国科学院微电子研究所 Method for preparing compound semiconductor sensitive membrane based on replacement reaction-thermal oxidation method
CN103128303A (en) * 2013-02-28 2013-06-05 北京科技大学 Method for preparing nanogold by vapor deposition process
CN104630772A (en) * 2013-11-12 2015-05-20 中国科学院物理研究所 Multilayer stacked metal nanosphere array and preparation method thereof
CN104357800B (en) * 2014-10-20 2017-02-15 西安交通大学 Nanometer silicon film cathode and manufacturing method thereof
CN104600102B (en) * 2014-12-24 2017-08-25 上海师范大学 A kind of Sb/Si heterostructure semiconductors nano-crystal film and preparation method and application
CN105862007B (en) * 2016-04-12 2018-08-10 西安交通大学 A method of generating Cu triangle crystal in Cu thin film systems

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1096061A (en) * 1993-05-29 1994-12-07 中国科学院金属研究所 Deposition of high melting metal carbonide nanometre crystal by sputtering
CN1128188A (en) * 1995-09-29 1996-08-07 中国科学院固体物理研究所 Size-controllable preparation method of nanometer-level silver
US6787434B1 (en) * 2003-04-01 2004-09-07 National Taiwan University Method of fabricating polysilicon film by nickel/copper induced lateral crystallization
CN1545152A (en) * 2003-11-26 2004-11-10 中国科学院上海微系统与信息技术研究 Method for preparing phase-changing film material nanometer wire
CN1552547A (en) * 2003-06-05 2004-12-08 中国科学院理化技术研究所 Preparing method for cubic silver nanometer grain
CN1654688A (en) * 2005-03-04 2005-08-17 东南大学 Method for preparing high density nano metal material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1096061A (en) * 1993-05-29 1994-12-07 中国科学院金属研究所 Deposition of high melting metal carbonide nanometre crystal by sputtering
CN1128188A (en) * 1995-09-29 1996-08-07 中国科学院固体物理研究所 Size-controllable preparation method of nanometer-level silver
US6787434B1 (en) * 2003-04-01 2004-09-07 National Taiwan University Method of fabricating polysilicon film by nickel/copper induced lateral crystallization
CN1552547A (en) * 2003-06-05 2004-12-08 中国科学院理化技术研究所 Preparing method for cubic silver nanometer grain
CN1545152A (en) * 2003-11-26 2004-11-10 中国科学院上海微系统与信息技术研究 Method for preparing phase-changing film material nanometer wire
CN1654688A (en) * 2005-03-04 2005-08-17 东南大学 Method for preparing high density nano metal material

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