CN101150115B - Conductive resistance blocking layer material for copper interconnection and making method - Google Patents
Conductive resistance blocking layer material for copper interconnection and making method Download PDFInfo
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- CN101150115B CN101150115B CN2007101852032A CN200710185203A CN101150115B CN 101150115 B CN101150115 B CN 101150115B CN 2007101852032 A CN2007101852032 A CN 2007101852032A CN 200710185203 A CN200710185203 A CN 200710185203A CN 101150115 B CN101150115 B CN 101150115B
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Abstract
This invention provides a conduction blocking material used in copper interlinkage composed of a silicon substrate and a conduction blocking layer characterizing that the material is formed by growing a non-crystal Ni-Al dual alloy film on the silicon substrate with a magnetic control sputter method and then growing a Cu film in-situ on the film, which can avoid diffusion to the Si substrate during the growth of Cu effectively since Ni-Al material and Si and Cu of good thermal dynamic stability are used here and non-crystal Ni-Al film does not include diffusion channels, besides, the magneticcontrol sputter method used in preparing the film can avoid reaction of Cu and Si under high temperature and play the role of blocking layer.
Description
Technical field
The present invention relates to a kind of barrier material and preparation method who is used for copper-connection, particularly suitable is used for the copper interconnection technology of very lagre scale integrated circuit (VLSIC), belongs to the manufacturing or the processing method technical field of microelectronic component or its parts.
Background technology
At present, integrated circuit technique develop rapidly arrives very lagre scale integrated circuit (VLSIC) (ULSI) stage, device performance is towards more high speed, low-power consumption direction develop, corresponding fine process has also entered the deep-submicron magnitude, makes the reliability of high-caliber interconnect technology become more and more for urgent simultaneously.Because metallic aluminium has film forming, graphical handling ease to realize that with silicon and the good characteristics of silicon dioxide adhesiveness, LSI and VLSI integrated circuit adopt the aluminium wiring technique more at present.But along with dwindling of microfabrication line size, the metallic aluminium ion in the aluminum interconnecting of energising can be migrated along the electron stream direction, this high temperature (T＞200 ℃) and high current density (j＞=10 of being transmitted in
6A/cm
2) effect under particularly remarkable.Experience hundreds of hour even after several hours, the cavity will appear in the aluminium wiring, and the cavity is assembled gradually and is caused ic failure, phenomenon that Here it is well-known " electric migration ".Along with improving constantly of integrated circuit integrated level, require the characteristic size of integrated circuit more and more littler, therefore, if still continue to adopt the aluminium wiring, will have a strong impact on the reliability of integrated circuit for ULSI.The resistivity of Cu is lower by 35% than Al, and in addition, the ion drift speed that Cu is caused by electricity under 275 ℃ condition is 1/65 of Al, and the stress characteristics of Cu also is much better than Al.Use the resistance of Cu interconnection can reducing on-chip interconnect, reduce the signal delay of coupled noise and interconnection line.Under the same RC time delay of maintenance, can reduce the number of plies of metal line, chip area can dwindle 20%～30% simultaneously.Though Cu has plurality of advantages, the introducing of Cu in microelectronics industry also has many problems to need to solve: (1) Cu can become deep-level impurity after diffusing into the Si substrate, influences the performance of device; (2) Cu and Si, Si0
2Poor adhesion; (3) Cu and Si react about 200 ℃ and form the compound of Cu and Si; (4) that works forms the oxide layer of self-protection unlike Al for Cu.Therefore, in copper interconnection technology,, need between Cu film and silicon substrate, introduce one deck diffusion impervious layer, to avoid direct contact the between Cu and the Si in order to prevent the above-described problem from occurring.The application need of Cu is with the discovery on desirable barrier layer and be applied as prerequisite.
Summary of the invention
The purpose of this invention is to provide that a kind of cost is low, thermodynamic stability good, intermetallic compound Ni-Al film good with Si substrate adhesiveness, that conductivity is good, fusing point is high is used for the copper-connection electrically conductive barrier, by selecting the magnetron sputtering technique parameter to realize the preparation on barrier layer, with the copper-connection of realizing following large scale integrated circuit to need for blocking layers.
Technical scheme of the present invention is achieved in that this electrically conductive barrier material that is used for copper-connection, form by silicon substrate, electrically conductive barrier, it is characterized in that: electrically conductive barrier material is to adopt the magnetron sputtering method amorphous state Ni-Al bianry alloy film of growing on the silicon substrate matrix, makes at Ni-Al bianry alloy film growth in situ Cu film material then.
The described electrically conductive barrier material that is used for copper-connection, described silicon substrate is the monocrystalline silicon of polishing, monocrystalline silicon that superficial growth has polysilicon and the substrate of other material.
The described electrically conductive barrier material that is used for copper-connection, described Ni-Al bianry alloy film thickness is 3-100nm.
The described electrically conductive barrier material that is used for copper-connection, described Cu film thickness is 5-300nm.
The described electrically conductive barrier material that is used for copper-connection, Ni-Al bianry alloy film of growing on the described silicon substrate matrix and Cu film are planar structure or damascene structure.
The described preparation method who is used for the electrically conductive barrier material of copper-connection comprises the steps:
A, the polishing monocrystalline substrate use HF, deionized water sonicated successively after, dry up on the sample stage that is placed into magnetron sputtering vacuum chamber with high pure nitrogen;
B, select the circular target of high-purity Ni-Al and Cu for use,,, respectively target is installed in after cleaning through acetone, absolute ethyl alcohol on the magnetic bases in the vacuum chamber to remove the impurity on target surface earlier with the surface of fine sand paper polishing target;
C, application molecular pump and vacuum pump are evacuated to (0.1-5) * 10 with the vacuum degree of vacuum chamber
-4Behind the Pa, the application traffic meter feeds high-purity argon gas in vacuum chamber, and keeping the air pressure of the high-purity argon dynamic equilibrium of vacuum chamber is 0.8-50Pa, and Ni-Al target and substrate spacing are 25-65mm, and sputtering power is 1-50W, and sedimentation time is 30min, obtains the Ni-Al noncrystal membrane;
After D, Ni-Al film preparation finish, do not open vacuum chamber, the vacuum degree of vacuum chamber is evacuated to (1-5) * 10
-4Behind the Pa, charge into high-purity argon gas in vacuum chamber, keeping the deposition pressure of vacuum chamber is 0.8-50Pa; Cu target and substrate spacing are 20-60mm, and sputtering power is 10-100W, rotate the sample stage growth in situ, the Cu film;
E, application high vacuum 1～5 * 10
-5The Pa annealing system carries out annealing in process to the CU/Ni-Al/Si multi-layer film structure, and annealing conditions is 300-900 ℃.
The described preparation method who is used for the electrically conductive barrier material of copper-connection, growth Cu depositing of thin film speed is 1-50nm/ minute among the step D.
The described preparation method who is used for the electrically conductive barrier material of copper-connection under 300-900 ℃ of temperature, directly uses the preparation that magnetron sputtering method is realized the Cu film among the step D, does not carry out annealing in process in addition.
The described preparation method who is used for the electrically conductive barrier material of copper-connection, step D after the Cu film of having grown, regrowth layer of Ni-Al passivation layer on the Cu film.
The present invention adopts magnetron sputtering method to prepare amorphous state Ni-Al film diffusion barrier layer on the semiconductor silicon substrate, the Cu film of further growing thereon.The Ni-Al material has good thermodynamic stability with Si and Cu; There is not diffusion admittance in the Ni-Al film of amorphous, can effectively avoid in the Cu growth course diffusion to silicon substrate; The Ni-Al film has that cost is low, thermodynamic stability good,, characteristics such as conductivity good, fusing point height good with Si substrate adhesiveness.Discover that amorphous Ni-Al film of using the magnetron sputtering method preparation can avoid Cu and Si to react when high annealing, play the function on the barrier layer that is used for copper-connection.The present invention is easy to control, equipment requirements is low, can with the semiconductor technology compatibility, be widely used in microelectronic.
Description of drawings
Fig. 1: the XRD figure of Cu/Ni-Al/Si spectrum under the different annealing temperature
To the sample of different temperatures annealing, in the drawings except the diffraction maximum of Cu, do not find that other dephasign peak exists, thereby the explanation layer with layer between do not have a chemical reaction.
Fig. 2: Cu/Ni-Al/Si face resistance is with the relation of annealing temperature
To the sample of different temperatures annealing, Cu/Ni-Al/Si face resistance does not significantly increase with the rising of annealing temperature, thus the explanation layer with layer between do not have chemical reaction and a counterdiffusion.
Fig. 3: Cu/Ni-Al/Si interface high resolution electron microscope figure
Cu/Ni-Al/Si interface high resolution electron microscope figure tells that we Ni-Al is a non crystalline structure, the interface is clear between layer and the layer, the atom of silicon substrate is as queueing discipline, further there are not chemical reaction and a counterdiffusion between proof layer and the layer, illustrated that Ni-Al can be used as the barrier material between Cu and the Si.
Embodiment
Embodiment 1:
1, the preparation of amorphous state Ni-Al film
1) (001) monocrystalline substrate of polishing with 10% HF, the cleaning of deionized water sonicated after, dry up with high pure nitrogen, put into rapidly on the sample stage of magnetron sputtering vacuum chamber;
2) select the circular target of high-purity Ni-Al and Cu for use, elder generation is with the surface of fine sand paper polishing target, to remove the impurity on target surface, through respectively target being installed in after acetone, the absolute ethyl alcohol cleaning on the magnetic bases in the vacuum chamber;
3) application molecular pump and vacuum pump are evacuated to (1-5) * 10 with the vacuum degree of vacuum chamber
-4Behind the Pa, the application traffic meter feeds high-purity argon gas in vacuum chamber, keeping the pressure of the high-purity argon dynamic equilibrium of vacuum chamber is 50Pa, use the radio frequency magnetron method of spattering and carry out the preparation of Ni-Al film, Ni-Al target (Beijing Tai Kenuo Co., Ltd) is 60mm with the substrate spacing, sputtering power is 5W, and sedimentation time is 20min, obtains the Ni-Al noncrystal membrane; The vacuum degree of vacuum chamber is evacuated to 1 * 10
-4Pa feeds high-purity argon gas then, and deposition pressure is 6Pa; The Ni-Al noncrystal membrane thickness 3.4nm that obtains;
2, the preparation of Cu film
1) on the Ni-Al noncrystal membrane basis of step 1 preparation, do not open vacuum chamber, the vacuum degree of vacuum chamber is evacuated to 1 * 10
-4Pa feeds high-purity argon gas then, and the control deposition pressure is 8Pa; Cu target (Beijing Tai Kenuo Co., Ltd) is 50mm with the substrate spacing, rotates the sample stage growth in situ, and sputtering power is 10-100W, and sedimentation time is 20min, and the Cu film thickness that obtains is 120nm;
2) above-mentioned sample is divided into the several piece small sample, under high vacuum condition 1～5 * 10
-5Pa carried out 300 ℃ one minute, 400 ℃ one minute, 600 ℃ one minute and 750 ℃ one minute to Cu film small sample in batches.To the sample of different temperatures annealing, Cu/Ni-Al/Si face resistance does not significantly increase with the rising of annealing temperature, as shown in Figure 2.
Embodiment 2:
1, the preparation of amorphous state Ni-Al film
1) (001) monocrystalline substrate of polishing with 10% HF, the cleaning of deionized water sonicated after, dry up with high pure nitrogen, put into rapidly on the sample stage of magnetron sputtering vacuum chamber;
2) select the circular target of high-purity Ni-Al and Cu for use, elder generation is with the surface of fine sand paper polishing target, to remove the impurity on target surface, through respectively target being installed in after acetone, the absolute ethyl alcohol cleaning on the magnetic bases in the vacuum chamber;
3) application molecular pump and vacuum pump are evacuated to (1-5) * 10 with the vacuum degree of vacuum chamber
-4Behind the Pa, the application traffic meter feeds high-purity argon gas in vacuum chamber, keeping the pressure of the high-purity argon dynamic equilibrium of vacuum chamber is 50Pa, use the radio frequency magnetron method of spattering and carry out the preparation of Ni-Al film, Ni-Al target (Beijing Tai Kenuo Co., Ltd) is 50mm with the substrate spacing, it is 50W that sputtering power is set, and sedimentation time is 25min, the Ni-Al noncrystal membrane thickness 100nm that obtains;
2, the preparation of Cu film
1) on the Ni-Al noncrystal membrane basis of step 1 preparation, do not open vacuum chamber, the vacuum degree of vacuum chamber is evacuated to 1 * 10
-4Pa feeds high-purity argon gas then, and the control deposition pressure is 8Pa; Cu target (Beijing Tai Kenuo Co., Ltd) is 50mm with the substrate spacing, rotates the sample stage growth in situ, and sputtering power is 100W, and sedimentation time is 9min, and the Cu film thickness that obtains is 300nm.
2) above-mentioned sample is divided into the several piece small sample, under high vacuum condition 1～5 * 10
-5Pa carried out 300 ℃ one minute, 400 ℃ one minute, 600 ℃ one minute and 750 ℃ one minute to Cu film small sample in batches, then the sample that obtains was detected.
Embodiment 3:
1, the preparation of amorphous state Ni-Al film
1) (001) monocrystalline substrate of polishing with 10% HF, the cleaning of deionized water sonicated after, dry up with high pure nitrogen, put into rapidly on the sample stage of magnetron sputtering vacuum chamber;
2) select the circular target of high-purity Ni-Al and Cu for use, elder generation is with the surface of fine sand paper polishing target, to remove the impurity on target surface, through respectively target being installed in after acetone, the absolute ethyl alcohol cleaning on the magnetic bases in the vacuum chamber;
3) application molecular pump and vacuum pump are evacuated to (1-5) * 10 with the vacuum degree of vacuum chamber
-4Behind the Pa, the application traffic meter feeds high-purity argon gas in vacuum chamber, keeping the pressure of the high-purity argon dynamic equilibrium of vacuum chamber is 50Pa, use the radio frequency magnetron method of spattering and carry out the preparation of Ni-Al film, Ni-Al target (Beijing Tai Kenuo Co., Ltd) is 60mm with the substrate spacing, sputtering power is 5W, and sedimentation time is 20min, obtains the Ni-Al noncrystal membrane; The vacuum degree of vacuum chamber is evacuated to 1 * 10
-4Pa feeds high-purity argon gas then, and deposition pressure is 6Pa; The Ni-Al noncrystal membrane thickness 4nm that obtains;
2, the preparation of Cu film
1) on the Ni-Al noncrystal membrane basis of step 1 preparation, do not open vacuum chamber, the vacuum degree of vacuum chamber is evacuated to 1 * 10
-4Pa feeds high-purity argon gas then, and the control deposition pressure is 8Pa; Cu target (Beijing Tai Kenuo Co., Ltd) is 50mm with the substrate spacing, rotates the sample stage growth in situ, and sputtering power is 10-100W, and sedimentation time is 0.8min, and the Cu film thickness that obtains is 5nm;
2) above-mentioned sample is divided into the several piece small sample, under high vacuum condition 1～5 * 10
-5Pa carried out 300 ℃ one minute, 400 ℃ one minute, 600 ℃ one minute and 750 ℃ one minute to Cu film small sample in batches, then the sample that obtains was detected.
The foregoing description growth Cu depositing of thin film speed may be selected to be 1-50nm/ minute.
The elongation technology scheme that the foregoing description provides is the preparation that can directly use high temperature 300-900 ℃ magnetron sputtering method realization Cu film, does not carry out annealing in process in addition.
The elongation technology scheme that the foregoing description provides is after the Cu film of having grown, regrowth layer of Ni-Al passivation layer on the Cu film.
Employed magnetic control sputtering system is many target systems of being produced by scientific instrument center, Shenyang in the foregoing description.
X-ray diffraction under each temperature of the foregoing description Cu/ amorphous state Ni-Al/Si heterojunction is measured and is not found that dephasign exists: as shown in Figure 1; Heterojunction boundary is carried out discovering that heterojunction boundary is clear, do not have counterdiffusion between the different materials, reacting to each other of transmission electron microscope and high resolution transmission electron microscopy: as shown in Figure 3, experimental result has fully shown with the feasibility of amorphous state Ni-Al film as copper interconnect barrier layer.
Listed examples of the present invention is intended to further illustrate barrier material and the preparation method who is used for copper-connection, and scope of the present invention is not constituted any restriction.
Claims (4)
1. the preparation method of a copper-connection, its feature comprises the steps:
A, the polishing monocrystalline substrate use HF, deionized water sonicated successively after, dry up on the sample stage that is placed into magnetron sputtering vacuum chamber with high pure nitrogen;
B, select the circular target of high-purity Ni-Al and Cu for use,,, respectively target is installed in after cleaning through acetone, absolute ethyl alcohol on the magnetic bases in the vacuum chamber to remove the impurity on target surface earlier with the surface of fine sand paper polishing target;
C, application molecular pump and vacuum pump are evacuated to (1-5) * 10 with the vacuum degree of vacuum chamber
-4Behind the Pa, the application traffic meter feeds high-purity argon gas in vacuum chamber, and keeping the air pressure of the high-purity argon dynamic equilibrium of vacuum chamber is 0.8-50Pa, and Ni-Al target and substrate spacing are 25-65mm, and sputtering power is 1-50W, and sedimentation time is 30min, obtains the Ni-Al noncrystal membrane;
After D, Ni-Al film preparation finish, do not open vacuum chamber, the vacuum degree of vacuum chamber is evacuated to (1-5) * 10
-4Behind the Pa, charge into high-purity argon gas in vacuum chamber, keeping the deposition pressure of vacuum chamber is 0.8-50Pa; Cu target and substrate spacing are 20-60mm, rotate the sample stage growth in situ, and sputtering power is 10-100W, and sedimentation time is 20min, obtains the Cu film;
E, application high vacuum (1-5) * 10
-5The Pa annealing system carries out annealing in process to the Cu/Ni-Al/Si multi-layer film structure, and annealing conditions is 300-900 ℃.
2. according to the preparation method of the described copper-connection of claim 1, it is characterized in that: growth Cu depositing of thin film speed is 1-50nm/ minute among the step D.
3. the preparation method of copper-connection according to claim 1 is characterized in that: directly use the preparation of high temperature 300-900 ℃ magnetron sputtering method realization Cu film, replace the feature of step D, do not carry out annealing in process in addition.
4. the preparation method of copper-connection according to claim 1 is characterized in that: step D after the Cu film of having grown, regrowth layer of Ni-Al passivation layer on the Cu film.
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| CN101150115B true CN101150115B (en) | 2010-09-29 |
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| CN102097367B (en) * | 2010-12-21 | 2013-07-17 | 河北大学 | Method for integrating Cu and ferric oxide functional film |
| CN103441118B (en) * | 2013-09-05 | 2016-04-13 | 河北大学 | A kind of electrically conductive barrier material for copper-connection and preparation method thereof |
| CN105039875B (en) * | 2015-08-24 | 2017-04-12 | 浙江大学 | Ni-Nb metal thin film with ultra-low roughness and preparation method of Ni-Nb metal thin film |
| CN106449425A (en) * | 2016-11-15 | 2017-02-22 | 华南理工大学 | High-conductivity interconnected electrode for display electronic devices and preparation method thereof |
| DE112017007985T5 (en) * | 2017-09-01 | 2020-06-04 | Intel Corporation | METAL CONNECTIONS, COMPONENTS AND METHOD |
| CN107768348B (en) * | 2017-09-25 | 2019-07-12 | 江苏时恒电子科技有限公司 | A kind of electrically conductive barrier material and preparation method thereof for copper interconnection |
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