CN101016616A - Method of preparing nanometer scale twin crystal copper thin film - Google Patents
Method of preparing nanometer scale twin crystal copper thin film Download PDFInfo
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- CN101016616A CN101016616A CN 200710037907 CN200710037907A CN101016616A CN 101016616 A CN101016616 A CN 101016616A CN 200710037907 CN200710037907 CN 200710037907 CN 200710037907 A CN200710037907 A CN 200710037907A CN 101016616 A CN101016616 A CN 101016616A
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Abstract
The invention discloses a preparing method of nanometer measure twin crystal copper film in microelectronic technical domain, which comprises the following steps: preparing a high interfacial energy underlay without easy to dissolve, diffuse and react with copper; using normal physics gas phase deposited method to deposit copper film; getting the nanometer measure twin crystal in the deposited copper film; or proceeding annealing treatment at proper temperature to increase the size of copper crystal grain and improve the density of copper twin crystal density. This invention possesses merits of simple, convenient and strong practicability.
Description
Technical field
The invention belongs to microelectronics technology, be specially a kind of preparation method of nanometer scale twin crystal copper thin film.
Background technology
The ideal electro-conductive material need possess high conductivity and high mechanical strength simultaneously.But widely used polycrystalline copper but has relatively poor physical strength in integrated circuit interconnection technology.Solid intensity depends on its elastoresistance deformability, and the elastic deformation of polycrystalline copper is because the motion of each intragranular position mistake produces usually.Can stop (comprising grain boundary, point defect etc.) motion of dislocation by the various defectives of artificial introducing, thereby improve the physical strength of copper, comprising reinforcement means such as solid fusion gold (metal-doped), cold working, grain refinings.But these based on the method for artificial introducing defective owing to increased the specific conductivity that the scattering of conduction electrons all will reduce copper, so ordinary method generally can not improve the specific conductivity and the physical strength of copper simultaneously.Find that a kind of effectively to suppress copper intragranular position Wrong Shipment copper microtexture moving and don't that increase the conduction electrons scattering be to improve the key of two kinds of performances of copper simultaneously.Twin boundary is a kind of low energy coherent grain boundary, and it can play strengthening effect as the effective minimizing dislocation motion of conventional grain boundary and avoid the scattering of increase to electronics simultaneously.Therefore by a large amount of copper twin boundaries of introducing, promptly prepare high-density twin copper, can both improve the physical strength of copper and don't the electroconductibility of loss copper.The method of human pulse platings such as Lu Ke has prepared nano twin crystal copper film on amorphous Ni film.And in the general report, physical vapour deposition preparation the copper film when about 1 micron of its thickness, just can observe significant twin.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nanometer scale twin crystal copper thin film simply and easily.
The preparation method of the nanometer scale twin crystal copper thin film that the present invention proposes is as follows: on silicon substrate, use physical gas-phase deposite method, at first prepare the substrate material that a kind of and Cu has high interfacial energy, this substrate also should have simultaneously and copper is difficult for the character of dissolving each other, spread, reacting.In general, C based compound and Cu have higher interfacial energy, as WC, and WCN, amorphous C films etc. can be used as substrate material.The material that other and Cu have high interfacial energy can use.For example can be chosen as the carbide of refractory metal, WC for example, TiC, TaC etc., the perhaps refractory metal ternary compound of carbon containing and nitrogen, WCN for example, TiCN, TaCN etc.This layer film thickness is not the factor of restriction, considers that from use angle the thickness of this layer film can be in the 5-100 nanometer.Use the physical vapour deposition method then, for example the sputtering method film of deposit layer of copper thereon more then can form the nanometer scale twin crystal structure in the copper film of deposit just, and the thickness of copper film generally can be 50-200nm.
For further increasing twin copper grain-size and improving copper twin density, the present invention also can further carry out anneal.Annealing temperature is a room temperature to 600 ℃, and annealing time is 30 seconds-2 minutes.
Because present method only needs to prepare specific substrate and just can prepare nanometer scale twin crystal copper thin film with the method for conventional physical vapour deposition, therefore have simple, convenient, practical characteristics.
Description of drawings
Fig. 1: scanning electronic microscope (SEM) picture of firm deposit sample.(a)Cu(100nm)/WC(10nm)/Si；(b)Cu(100nm)/W(10nm)/Si。
Fig. 2: the scanning electronic microscope of annealing specimen (SEM) picture.(a) Cu (100nm)/WC (10nm)/Si, (annealing in 60 seconds of 510 degree) is Cu (100nm)/W (10nm)/Si (b), (annealing in 60 seconds of 550 degree).
EBSD (EBSD) analysis chart of Fig. 3: sample Cu (100nm)/WC (10nm)/Si (annealing in 60 seconds of 510 degree), the left side is the SEM figure of sample, the right is the crystal orientation mapping color diagram of corresponding institute favored area, and red area shows that to green area adjacent crystal grain rotates 60 degree each other along＜111〉crystal orientation.
Fig. 4: Cu (100nm)/WCN (10nm)/60 seconds annealed scanning electronic microscope (SEM) pictures of Si sample 550 degree.
Embodiment
Embodiment 1
1: selecting silicon (Si) is substrate, through standard RCA cleaning and after hydrofluoric acid (HF) solution of finite concentration (generally adopting 2%) cleans the removal native oxide layer, physical vapour deposition (PVD) the equipment cavity of packing into, base vacuum is low more good more, and the vacuum tightness that provides in this example is 2 * 10
-5Pa.Use magnetic control co-sputtering method deposit one deck wolfram varbide (WC) film thereon.The thickness of WC film is unrestricted, and from the technology simplicity, the film thickness that adopts in this example is 10 nanometers.Feed Ar gas during deposit, operating air pressure is 5 * 10
-1Pa.
2: do not destroying under the vacuum condition, continuing the copper film of magnetron sputtering deposit one deck 100nm, operating air pressure is 5 * 10 during deposit
-1Pa.Obtain the sample structure of Cu (100nm)/WC (10nm)/Si, promptly have the twin structure of nanoscale in the copper film of this moment of deposit just, shown in accompanying drawing 1 (a).The distinctive striped of twin structure can be observed by clear.
3: sample Cu (100nm)/WC (10nm)/Si is carried out anneal, and temperature can be between room temperature to 600 ℃, and annealing atmosphere can be protection of inert gas or vacuum.Adopt 510 ℃ of nitrogen protections to anneal 60 seconds down in this example, copper grain-size and twin copper density all increase, shown in accompanying drawing 2 (a).
Get sample shown in the accompanying drawing 2 (a) and carry out the textural property of EBSD (EBSD) analysis, as shown in Figure 3 with research copper twin.The twin that the EBSD analysis revealed is adjacent rotates 60 each other along＜111〉crystal orientation and spends, and the spacing of twin is about the 20-150 nanometer.
Embodiment 2
1: selecting silicon (Si) is substrate, through standard RCA cleaning and after hydrofluoric acid (HF) solution of 2% concentration cleans the removal native oxide layer, physical vapour deposition (PVD) the equipment cavity of packing into, base vacuum is low more good more, and the vacuum tightness that provides in this example is 2 * 10
-5Pa.Use thick carbon tungsten nitride (WCN) film of magnetic control co-sputtering method deposit one deck 10nm～100nm thereon.Sputtering atmosphere is nitrogen and argon gas mixed gas, and nitrogen argon partial pressure ratio is 1: 4, and the deposition rate ratio of carbon target and tungsten target is 3: 7, and operating air pressure is 5 * 10 during deposit
-1Pa.
2: do not destroying under the vacuum condition, continuing the copper film of magnetron sputtering deposit one deck 100nm, operating air pressure is 5 * 10 during deposit
-1Pascal.Obtain the sample structure of Cu (100nm)/WCN (10nm)/Si.Further sample is carried out anneal, select 550 ℃ of rapid thermal annealings 90 seconds, shown in the accompanying drawing 4, twin striation can be observed equally.
Comparative example 1
1: selecting silicon (Si) is substrate, through standard RCA cleaning and after hydrofluoric acid (HF) solution of 2% concentration cleans the removal native oxide layer, and the physical vapour deposition of packing into (PVD) equipment cavity, the base vacuum degree is 2 * 10
-5Pa.Use thick tungsten (W) film of magnetically controlled sputter method deposit one deck 10nm thereon, operating air pressure is 5 * 10 during deposit
-1Pa.
2: do not destroying under the vacuum condition, continuing the copper film of magnetron sputtering deposit one deck 100nm, operating air pressure is 5 * 10 during deposit
-1Pa.Obtain the sample structure of Cu (100nm)/W (10nm)/Si, in the copper film of deposit just, can not observe twin striation, shown in accompanying drawing 1 (b).
3: select 550 degrees centigrade of 60 seconds rapid thermal annealings that sample Cu (100nm)/W (10nm)/Si is carried out anneal, twin striped still can not be observed, shown in accompanying drawing 2 (b).This is because W substrate and Cu have lower interfacial energy.
Claims (4)
1. the preparation method of a nanometer scale twin crystal copper thin film is characterized in that concrete steps are as follows:
(1) on silicon substrate, prepare the substrate that a kind of and Cu has high interfacial energy with physical gas-phase deposite method, this substrate also has simultaneously and copper is difficult for the character of dissolving each other, spread, reacting, and substrate thickness is 10-100nm;
(2) then, on this substrate,, can form nanometer scale twin crystal in the copper film of deposit just with the method deposit layer of copper film of physical vapour deposition.
2. the preparation method of nanometer scale twin crystal copper thin film according to claim 1, the material that it is characterized in that described substrate is the carbide of refractory metal, perhaps is the refractory metal ternary compound of carbon containing and nitrogen.
3. the preparation method of nanometer scale twin crystal copper thin film according to claim 2, the material that it is characterized in that described substrate is WC, TiC, TaC, or be WCN, TiCN, TaCN.
4. the preparation method of nanometer scale twin crystal copper thin film according to claim 1 is characterized in that also further carrying out anneal, and annealing temperature is a room temperature to 600 ℃, and annealing time is 30 seconds to 2 minutes.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101403096B (en) * | 2008-11-06 | 2010-06-02 | 哈尔滨工程大学 | Method of producing nano-twin crystal aluminum surface film material with high corrosion resistance |
| TWI455663B (en) * | 2012-10-16 | 2014-10-01 | Univ Nat Chiao Tung | Circuit board with twinned cu circuit layer and method for manufacturing the same |
| CN104392939A (en) * | 2014-10-27 | 2015-03-04 | 中国科学院上海微系统与信息技术研究所 | Nanotwinned copper redistribution wire manufacturing method |
| CN104841939A (en) * | 2015-04-27 | 2015-08-19 | 中国人民解放军装甲兵工程学院 | Preparation method for highly exothermic self-propagating combustion nanometer composite powder |
| CN106298634A (en) * | 2015-05-15 | 2017-01-04 | 中国科学院金属研究所 | The method for filling through hole of a kind of oriented growth nano twin crystal copper and application thereof |
| CN113260739A (en) * | 2018-10-31 | 2021-08-13 | 朗姆研究公司 | Electrodeposition of nano-twin copper structures |
| CN114411233A (en) * | 2022-01-11 | 2022-04-29 | 大连理工大学 | Method for rapidly preparing (100) single crystal copper |
Families Citing this family (1)
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| TWI731293B (en) | 2019-01-18 | 2021-06-21 | 元智大學 | Nanotwinned structure |
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2007
- 2007-03-08 CN CNB2007100379075A patent/CN100503880C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101403096B (en) * | 2008-11-06 | 2010-06-02 | 哈尔滨工程大学 | Method of producing nano-twin crystal aluminum surface film material with high corrosion resistance |
| TWI455663B (en) * | 2012-10-16 | 2014-10-01 | Univ Nat Chiao Tung | Circuit board with twinned cu circuit layer and method for manufacturing the same |
| CN104392939A (en) * | 2014-10-27 | 2015-03-04 | 中国科学院上海微系统与信息技术研究所 | Nanotwinned copper redistribution wire manufacturing method |
| CN104392939B (en) * | 2014-10-27 | 2017-09-01 | 中国科学院上海微系统与信息技术研究所 | The preparation method that nano twin crystal copper is connected up again |
| CN104841939A (en) * | 2015-04-27 | 2015-08-19 | 中国人民解放军装甲兵工程学院 | Preparation method for highly exothermic self-propagating combustion nanometer composite powder |
| CN106298634A (en) * | 2015-05-15 | 2017-01-04 | 中国科学院金属研究所 | The method for filling through hole of a kind of oriented growth nano twin crystal copper and application thereof |
| CN113260739A (en) * | 2018-10-31 | 2021-08-13 | 朗姆研究公司 | Electrodeposition of nano-twin copper structures |
| CN114411233A (en) * | 2022-01-11 | 2022-04-29 | 大连理工大学 | Method for rapidly preparing (100) single crystal copper |
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| CN100503880C (en) | 2009-06-24 |
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