CN103266304A - Preparation method of diffusion impervious layer free Cu(Ru) alloy material with high thermal stability - Google Patents
Preparation method of diffusion impervious layer free Cu(Ru) alloy material with high thermal stability Download PDFInfo
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Abstract
The invention relates to a preparation method of a diffusion impervious layer free Cu(Ru) alloy material with high thermal stability. The method is characterized by comprising the following steps: using a single crystal Si(111) wafer as a substrate material; selecting a high-purity Cu target and a high-purity Ru target; fixing the power of the Cu target at 80+/-10; changing the sputtering power of the Ru target in a range of (3-15)+/-1W so as to change the content of solid solution phase Ru in a Cu(Ru) alloy interconnecting material; and obtaining the alloy material through a direct current magnetic control confocal sputtering method. The diffusion impervious layer free Cu(Ru) alloy material with high thermal stability can be obtained, excellent electric performance can be maintained, and the actual application of the alloy material is better ensured. The method provided by the invention is simple to operate, good in repeatability and excellent in implementing effect.
Description
Technical field
The present invention relates to a kind of high thermal stability does not have the preparation of diffusion impervious layer Cu (Ru) alloy interconnect material.
Background technology
Along with the microminiaturized and intensive development of super large-scale integration, characteristic dimension continues to reduce, because copper has favorable conductive and electric migration performance with respect to aluminium, thereby copper has replaced aluminium and has become main interconnection material in super large-scale integration (ULSI) is made.In order to prevent that Cu from diffusing into the sticking power that causes in the Si base substrate that device performance descends and improves Cu and Si base substrate, need between Cu interconnection line and Si substrate, deposit one deck diffusion impervious layer, the interconnection structure of preparation Cu/ blocking layer/Si, deposition one deck blocking layer between copper silicon, and then the very thin copper seed layer of deposition one deck is as the conducting medium of electro-coppering, also as the crystal nucleation layer of the Metallic Solids growth of electro-coppering.Technology then is that chemical machinery polishes (CMP), grinds off unnecessary copper, and silicon chip surface is polished.
Along with the yardstick of semiconducter device is more and more littler, the blocking layer also becomes obvious further to the influence of device electric property in the copper interconnect structures.The defective of widely used Cu/ blocking layer/Si interconnection structure under 32nm technology and lower yardstick is obvious further in the traditional industry.At first surface irregularity and the resistance owing to barrier material is bigger, thus before follow-up galvanic deposit Cu layer, need to deposit thicker Cu inculating crystal layer, thus cause the size of whole copper interconnect structures can't accomplish very little.Secondly the resistance on blocking layer has also influenced the electric property of whole copper interconnect structures greatly.Therefore, how the more excellent copper interconnect structures of processability substitutes traditional Cu/ blocking layer/Si interconnection structure becomes the technical barrier that needs to be resolved hurrily at present.
At present a kind of emerging unobstructed layer interconnection structure is subjected to scholar's extensive concern in recent years.Direct deposited copper alloy layer and do not deposit diffusion impervious layer in advance and prepare copper alloy/Si interconnection structure on the Si substrate in the unobstructed layer interconnection structure replaces traditional Cu/ blocking layer/Si interconnection structure.This unobstructed layer interconnection structure not only simplified preparation technology but also greatly reduced the technology cost, also has good high high-temp stability and excellent electric property simultaneously.
The doped element that is suitable as the copper alloy interconnection structure need meet the following conditions: (1) element itself does not have radioactivity, bio-toxicity; (2) the easy and Cu element doping of element; (3) doped element has lower solid solubility in Cu, can separate out in the process of annealing, thereby reduce solid solution phase to the influence of interconnection structure resistance.
In sum, how to prepare Cu (Ru) the alloy interconnect material with high thermal stability and become of crucial importance, also directly influenced its reliability in actual applications.The Ru constituent content also can directly influence the electric property of interconnection structure in Cu (Ru) alloy.
Summary of the invention
The purpose of this invention is to provide a kind of high thermal stability does not have the preparation method of diffusion impervious layer Cu (Ru) alloy material, adjust the Ru content of Cu (Ru) alloy firm by the Ru target power in the control magnetron sputtering process, obtain having unobstructed layer Cu (Ru) the alloy interconnect structure of excellent electric property and barrier properties, can stop the diffusion of copper atom effectively, significantly reduce processing step, reduce preparation cost.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
High thermal stability does not have the preparation method of diffusion impervious layer Cu (Ru) alloy material, adopts the confocal sputtering method preparation of direct magnetic control to have Cu (Ru) membrane structure of different Ru content.Sputtering target material is that purity reaches 99.99wt% above Cu and Ru, and substrate is single crystalline Si sheet (111), before deposition, the Si sheet is cleaned through dehydrated alcohol and acetone, puts into the sample table of vacuum chamber then immediately.
Significant parameter is: before preparation Cu (Ru) alloy material, take out base vacuum to 6 * 10 earlier
-5Pa, feed Ar gas then, flow is 20sccm, and regulating vacuum degree in vacuum chamber by slide valve is 3.5Pa, begins airglow then, for the spot of removing Cu and Ru target material surface and oxide compound etc., guarantee the purity of film, will carry out about 30 minutes pre-sputter earlier, after the pre-sputter, vacuum tightness is transferred to about 1.5Pa operating air pressure, Cu (Ru) alloy interconnect material begins to grow again.The sputtering power of Cu target is fixed as 80 ± 10W.For Cu (Ru) alloy material that grows different Ru content, we realize that by Ru target as sputter power in the adjusting sputter procedure scope of sputtering power is (3-15) ± 1W, and underlayer temperature is room temperature.Cu (Ru) the alloy interconnect material thickness of preparation is respectively 300 ± 10nm.
The invention provides the accurately controlled method for preparing unobstructed layer Cu (Ru) alloy interconnect material of a kind of Ru content, do not deposit diffusion impervious layer in advance, but directly deposit Cu (Ru) alloy at the Si substrate, utilize the solid solution phase Ru element in Cu (Ru) alloy to reach the purpose that stops Cu atom interconnection diffusion, the Ru atom of Cu (Ru) alloy intermediate gap can be separated out in the process of high temperature annealing in addition, the Ru atom of separating out has further reduced the influence of solid solution phase to interconnection structure resistance, has improved the electric property of Cu (Ru) alloy interconnect material.
The higher vacuum tightness that the dc sputtering that adopts has not only can effectively guarantee the purity of Cu and Ru film, prevents that foreign gas from polluting it, has also effectively guaranteed the intrinsic physicals of Cu (Ru) alloy interconnect material simultaneously.By the accurate adjusting to the Ru target power output, realized the control of Ru content in Cu (Ru) the alloy interconnect material preferably, guaranteed its stability in actual applications.
The Ru element is a kind of emerging barrier material.Ru is the same with Ta have high-melting-point, high-temperature stability and and Cu good characteristics such as chemical reaction do not take place.In addition, Ru also has the not available good characteristic of Ta.The body resistivity of Ru is 7.6 μ Ω cm, approximately is half of Ta resistivity, therefore as the metal-doped influence that can reduce greatly interconnection structure resistance of solid solution.
Compare with existing preparation method, the present invention has following beneficial effect:
1. the present invention is the method that is prepared under a kind of condition of high vacuum degree, can effectively avoid film oxidized.The target purity that adopts is more than 99.99%.Metal Ru very easily oxidation in air in addition, the primary Ru oxide compound of formation can reduce Cu (Ru) alloy interconnect material purity, make interconnection structure very fast inefficacy in the process under arms.In our preparation, can avoid the oxidation of Ru film fully, guarantee the quality of prepared film.
2. the present invention can realize the accurate control to Ru constituent content in Cu (Ru) the alloy interconnect material.The method of control is simple and easy to control, and only need regulate the Ru target power in the process of sputter, and repeatability is also better.
3. the present invention can realize Cu (Ru) alloy interconnect material thickness is accurately controlled.Under identical processing parameter, depositing of thin film velocity-stabilization, good reproducibility.Thickness can be controlled at nanoscale.
4. preparation technology of the present invention is simple and convenient, and controllability is good.
5. the present invention can realize the accurate control of Ru content in Cu (Ru) the alloy interconnect material is obtained high performance diffusion barrier property, and maximum operating temperature can reach 550 ℃.
Description of drawings
Fig. 1 deposits surperficial SEM pattern and the EDX composition analysis of attitude Cu (Ru) film;
Fig. 2 deposits the XRD analysis of Cu (Ru) interconnection structure after attitude and the 350-650 ℃ of annealing;
Cu (Ru) interconnection structure resistivity was analyzed and Ru element XPS surface analysis after Fig. 3 deposited attitude and 350-650 ℃ of annealing.
Embodiment
Adopt direct current magnetron sputtering process to prepare Cu (Ru) alloy material of different Ru content, a model is the magnetic control sputtering device of JGP450, and this equipment uses the permanent magnetism target, and diameter 75mm only adds direct supply, and maximum sputtering power is 500W.Sample rotating disk with rotation function, but sample both can heat also water-cooled, top temperature can arrive 550 ℃, and the heating rate variable range is at 10 ℃/min-40 ℃/min.Three targets are confocal in sample table, are applicable to laminated film and the multilayer film of the multiple differing materials of preparation.The vacuum system maximum vacuum can reach 6.6 * 10
-5Pa, the vacuum tightness of superelevation has effectively been protected the quality of film.
Material is prepared: sputtering target material is that purity reaches 99.999%Cu and 99.99%Ru, and diameter 75mm, the about 3mm of thickness, substrate are single crystalline Si (111).In order to improve the sticking power of Cu (Ru) alloy material and substrate, before deposition, the Si sheet is cleaned and ultrasonic 30 minutes by ethanol, acetone successively, with surface dirt and the oil stain of removing the adhesion that influences film and substrate.Before sputter, earlier target is carried out about 30 minutes pre-sputter in addition, remove its surperficial zone of oxidation and spot, guaranteed the purity of film, also provide guarantee for the quality that guarantees film.
The significant parameter that direct current magnetron sputtering process prepares different Ru content Cu (Ru) alloy interconnect material is: before preparation Cu (Ru) alloy material, take out base vacuum to 6 * 10 earlier
-5Pa, feed Ar gas then, flow is 20sccm, and regulating vacuum degree in vacuum chamber by slide valve is 3.5Pa, begins airglow then, for the spot of removing Cu and Ru target material surface and oxide compound etc., guarantee the purity of film, will carry out about 30 minutes pre-sputter earlier, after the pre-sputter, vacuum tightness is transferred to about 1.5Pa operating air pressure, Cu (Ru) alloy interconnect material begins to grow again.The sputtering power of Cu target is fixed as 80 ± 10W.For Cu (Ru) alloy material that grows different Ru content, we realize that by Ru target as sputter power in the adjusting sputter procedure scope of sputtering power is (3-15) ± 1W, and underlayer temperature is room temperature.Cu (Ru) the alloy interconnect material thickness of preparation is respectively 300 ± 10nm.
The preparation of Cu (Ru) alloy material: adopt the confocal sputtering method of direct magnetic control, base vacuum is evacuated to 6 * 10
-5Pa, the Ar airshed is 20sccm, operating pressure is set to 1.5Pa.Fixation of C u target power output is 80 ± 10W in the control sputter procedure, comes the content of Ru in accuracy controlling Cu (Ru) alloy material by power (the 3-15) ± 1W that changes the Ru target.Control the thickness of film according to sputtering time, the thickness of Cu (Ru) alloy material is 300 ± 10nm.Substrate temperature remains 150 ℃ in the experiment.
Structural characterization and result:
By to the surperficial SEM pattern of deposition attitude Cu (Ru) film and EDX composition analysis (Fig. 1) as can be known, when Ru power was 5W, the crizzle of Cu (Ru) alloy was minimum.By to the EDX elemental composition analysis in deposition attitude Cu (Ru) alloy as can be known, change from 3-15W at the Ru target power output, Ru content in Cu (Ru) alloy increases gradually with the increase of Ru power, and Ru content is about 1.88% during 3W, and Ru content was about 6.15% when power was increased to 15W.By to deposition attitude Cu (Ru) alloy XRD analysis as can be known, Cu (Ru) alloy film is nanocrystalline, and the average grain size that can calculate Cu (Ru) alloy according to the Scherrer formula is about 30 ± 5nm.
The unobstructed layer of Cu (Ru) interconnection structure carried out 350-650 ℃, the 30 minutes XRD analysis results behind the annealing test show (Fig. 2): the Ru element doping can improve the barrier properties of Cu (Ru) alloy, at 450 ℃, Cu in the time of 550 ℃ (Ru) alloy still keeps good barrier properties, and resistance slightly rises.Cu (Ru) alloy barrier performance sharply descends after 650 ℃ of annealing, a plurality of Cu occur
3The diffraction peak of Si phase, and resistance rises rapidly.By Ru3d XPS collection of illustrative plates (Fig. 3) in Cu (Ru) alloy after deposition attitude, 550 ℃ and the 650 ℃ of annealing is offset to high bound energy direction at the Ru3d peak as can be known, the Ru atom that solid solution in Cu (Ru) alloy of annealing back is described is therefrom separated out, and has caused the variation of Ru3d bound energy.Summarize describedly, the thermostability that the mixing of Ru element can be improved Cu (Ru) alloy and interconnection structure still keep good electric property (and Ru content is low, cost is low).Above-mentioned embodiment does not limit technical scheme of the present invention in any form, and every employing is equal to replaces or technical scheme that the mode of equivalent transformation obtains all drops on protection scope of the present invention.
Claims (4)
1. high thermal stability does not have the preparation method of diffusion impervious layer Cu (Ru) alloy material, it is characterized in that it being as substrate material with single crystalline Si (111) sheet, select high-purity Cu target and Ru target for use, fixation of C u target power output is 80 ± 10W, the content of solid solution phase Ru in the sputtering power of change Ru target and then change Cu (Ru) the alloy interconnect material obtains by the confocal sputtering method of direct magnetic control in (3-15) ± 1W scope.
2. high thermal stability according to claim 1 does not have the preparation method of diffusion impervious layer Cu (Ru) alloy material, it is characterized in that the magnetic control sputtering device that the confocal sputtering method of direct magnetic control adopts takes out base vacuum to 6 * 10 earlier
-5Pa feeds Ar gas then, and the Ar airshed is 20sccm, and operating pressure is set to 3.5Pa during pre-sputter; When sputter, vacuum tightness is transferred to about 1.5Pa operating air pressure.
3. high thermal stability according to claim 1 does not have the preparation method of diffusion impervious layer Cu (Ru) alloy material, it is characterized in that described substrate cleans before deposition, and substrate temperature is 150 ℃ during sputter.
4. high thermal stability according to claim 1 does not have the preparation method of diffusion impervious layer Cu (Ru) alloy material, it is characterized in that before sputter, earlier target is carried out pre-sputter.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630711A (en) * | 2015-01-28 | 2015-05-20 | 西安交通大学 | Preparation method of plastic metallic nano Cu/Ru multilayer film |
| CN111519133A (en) * | 2020-05-19 | 2020-08-11 | 昆明贵金属研究所 | Ti material with good-binding-property antioxidant coating and preparation method thereof |
| US10847463B2 (en) | 2017-08-22 | 2020-11-24 | Applied Materials, Inc. | Seed layers for copper interconnects |
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| US20090186230A1 (en) * | 2007-10-24 | 2009-07-23 | H.C. Starck Inc. | Refractory metal-doped sputtering targets, thin films prepared therewith and electronic device elements containing such films |
| CN101597751A (en) * | 2009-04-22 | 2009-12-09 | 江苏科技大学 | Zr-Al-Si-N hard composite coating and preparation method thereof |
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Patent Citations (2)
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| US20090186230A1 (en) * | 2007-10-24 | 2009-07-23 | H.C. Starck Inc. | Refractory metal-doped sputtering targets, thin films prepared therewith and electronic device elements containing such films |
| CN101597751A (en) * | 2009-04-22 | 2009-12-09 | 江苏科技大学 | Zr-Al-Si-N hard composite coating and preparation method thereof |
Non-Patent Citations (1)
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| CHU,J.P等: "Cu films containing insoluble Ru and RuNx on barrierless Si for excellent property improvements", 《APPLIDE PHYSICS LETTERS》, vol. 91, no. 13, 27 September 2007 (2007-09-27), XP 012099400, DOI: doi:10.1063/1.2790843 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630711A (en) * | 2015-01-28 | 2015-05-20 | 西安交通大学 | Preparation method of plastic metallic nano Cu/Ru multilayer film |
| CN104630711B (en) * | 2015-01-28 | 2017-04-26 | 西安交通大学 | Preparation method of plastic metallic nano Cu/Ru multilayer film |
| US10847463B2 (en) | 2017-08-22 | 2020-11-24 | Applied Materials, Inc. | Seed layers for copper interconnects |
| CN111519133A (en) * | 2020-05-19 | 2020-08-11 | 昆明贵金属研究所 | Ti material with good-binding-property antioxidant coating and preparation method thereof |
| CN111519133B (en) * | 2020-05-19 | 2022-03-04 | 昆明贵金属研究所 | Ti material with good-binding-property antioxidant coating and preparation method thereof |
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