CN103377988B - Method for preventing copper diffusion - Google Patents
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- CN103377988B CN103377988B CN201210113569.XA CN201210113569A CN103377988B CN 103377988 B CN103377988 B CN 103377988B CN 201210113569 A CN201210113569 A CN 201210113569A CN 103377988 B CN103377988 B CN 103377988B
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Abstract
A method for preventing copper diffusion comprises providing a semiconductor substrate, wherein a dielectric layer is formed on the semiconductor substrate and a copper interconnection line is positioned I the dielectric layer and the surface of the copper interconnection line is exposed; and bombarding the surface of the copper interconnection line through inert gas plasmas. According to the method for preventing copper diffusion, bombardment on the surface of the copper interconnection line in the dielectric layer formed on the semiconductor substrate is performed through the inert gas plasmas, and thus stress inside the copper interconnection line is released, crystal grains inside the copper interconnection line are thinned, and copper atoms in the copper interconnection line are prevented from generating stress migration; in addition, the bombardment on the copper interconnection line through the inert gas plasmas can enable the surface of the copper interconnection line to be non-crystallized, enable the copper atoms to not migrate easily in the direction of a crystal face, and electrical performance of a device containing the copper interconnection line is improved.
Description
Technical field
The present invention relates to technical field of manufacturing semiconductors, concrete, the present invention relates to a kind of method preventing copper from spreading.
Background technology
Compared with conventional interconnect materials of aluminum, because copper has higher conductivity and better electromigration resistance properties, so be widely used at present in the interconnection line of very lagre scale integrated circuit (VLSIC).But copper is rapid diffusion in dielectric layer easily, very high leakage current and dielectric layer may be caused to puncture, for this reason, need between copper interconnecting line and dielectric layer, arrange the barrier layer preventing copper from spreading.Along with the development of very lagre scale integrated circuit (VLSIC), the particularly continuous reduction of programmable logic device size, still there is copper with the dielectric layer between layer adjacent interconnection line and to enter diffusion wherein from interconnection line top, this copper diffusion makes dielectric layer very easily puncture.
According to the feature that dielectric layer punctures, two types can be divided into by puncturing.One is intrinsic breakdown, and namely voltage one is added in copper interconnection structure, and electric field strength just meets or exceeds the dielectric layer breakdown critical field intensity of copper interconnection structure, and the electric current in dielectric layer becomes very large instantaneously, and dielectric layer is at once breakdown.Another kind is time correlation dielectric breakdown (the Time Dependent Dielectric Breakdown relevant to reliability, TDDB), namely electric field on dielectric layer is applied to lower than its intrinsic breakdown field intensity, do not cause intrinsic breakdown, but after experience certain hour, dielectric layer still there occurs and punctures.
Cause with the reason of time correlation dielectric breakdown is because the integrated level of chip improves, interconnection line becomes very thin, in the energized state, current density is wherein very large, under higher current density effect, metal ion in interconnection line metal level can move in the other direction along electron motion, this phenomenon is referred to as electromigration, electromigration can make metal level pile up (Pileup) and occur hillock (Hillocks) at regional area by quality because of the migration of metal ion, or there is cavity (Voids) by mass defect and the device that causes or interconnection performance degradation even lost efficacy.
Therefore, the loss of copper ion in copper interconnecting line metal level is suppressed can to improve and time correlation dielectric breakdown.Because copper interconnecting line can touch oxidizability etching gas in forming process, and can expose in atmosphere unavoidably, so the copper atom on copper surface very easily oxidized formation CuO, also have relevant report to adopt N at present
2or H
2plasma reduction copper ion Cu, refers to the people such as Tsung-Kuei Kang and was published in the article that exercise question on Journal of The Electrochemical Society is Avoiding Cu Hillocks during the Plasma Process in 2004.But, adopt N
2or H
2the principle of plasma reduction be based on: plasma is under high pressure ionized into ion atoms etc., reduction reaction is there is with copper interconnecting line surface, CuO is reduced into Cu, but metallic atom still plays pendulum, to suppressing the loss of copper ion and improving and time correlation dielectric breakdown DeGrain.
Therefore, propose a kind of method preventing copper from spreading, to suppress the loss of copper ion in copper interconnecting line, improve and become one of current problem demanding prompt solution with time correlation dielectric breakdown.
Summary of the invention
The problem that the present invention solves is to provide a kind of method preventing copper from spreading, and to suppress copper ion in copper interconnecting line to run off, improves the time correlation dielectric breakdown relevant to device reliability.
For solving the problem, the invention provides a kind of method preventing copper from spreading, comprising:
Semiconductor substrate is provided, described Semiconductor substrate is formed with dielectric layer and is positioned at described dielectric layer and the copper interconnecting line that comes out of surface;
By inert gas plasma, described copper interconnecting line surface is bombarded.
Optionally, before described copper interconnecting line surface being bombarded by inert gas plasma, also comprise: by hydrogen gas plasma, described copper interconnecting line surface is bombarded.
Optionally, when being bombarded described copper interconnecting line surface by hydrogen gas plasma, the flow of hydrogen is within the scope of 100 ~ 2000sccm, and pressure is within the scope of 1 ~ 7torr, and power is within the scope of 100 ~ 15000w, and the time is within the scope of 1 ~ 20s.
Optionally, described inert gas is helium, when being bombarded described copper interconnecting line surface by helium gas plasma, the flow of helium is within the scope of 100 ~ 2000sccm, pressure is within the scope of 1 ~ 7torr, and power is within the scope of 100 ~ 15000W, and the time is within the scope of 1 ~ 20s.
Optionally, described inert gas is argon gas, when being bombarded described copper interconnecting line surface by argon plasma, the flow of argon gas is within the scope of 100 ~ 2000sccm, pressure is within the scope of 1 ~ 7torr, and power is within the scope of 100 ~ 15000W, and the time is within the scope of 1 ~ 20s.
Optionally, by inert gas plasma, bombardment is carried out to described copper interconnecting line surface and comprise: first by helium gas plasma, described copper interconnecting line surface is bombarded, then by argon plasma, described copper interconnecting line surface is bombarded.
Optionally, when being bombarded described copper interconnecting line surface by helium gas plasma, the flow of helium is within the scope of 100 ~ 1000sccm, and pressure is within the scope of 1 ~ 7torr, and power is within the scope of 500 ~ 1500W, and the time is within the scope of 10 ~ 20s; When being bombarded described copper interconnecting line surface by argon plasma, the flow of argon gas is within the scope of 100 ~ 1000sccm, and pressure is within the scope of 1 ~ 7torr, and power is within the scope of 500 ~ 1500W, and the time is within the scope of 10 ~ 20s.
Optionally, after described copper interconnecting line surface being bombarded by inert gas plasma, also comprise: form the barrier layer covering described dielectric layer and copper interconnecting line surface.
Optionally, the material on described barrier layer is nitrogen-doped silicon carbide.
Optionally, the thickness on described barrier layer is within the scope of 150 ~ 500 dusts.
Compared with prior art, the present invention has the following advantages:
(1) method that the present invention prevents copper from spreading is bombarded the copper interconnecting line surface be formed in Semiconductor substrate in dielectric layer by inert, plasma, make the Stress Release of copper interconnecting line inside, the size of refinement copper interconnecting line internal grain, prevents copper atom generation stress migration in copper interconnecting line; In addition, by inert gas plasma, bombardment is carried out to copper interconnecting line and the surface of copper interconnecting line can also be made decrystallized, copper atom is not easily moved along crystal plane direction, improves the electric property of the device comprising described copper interconnecting line.
(2) as preferred embodiment, the present invention is first bombarded interconnection line surface by the helium plasma that molecule is less, by the argon plasma that molecule is larger, copper interconnecting line surface is bombarded again, while making copper interconnecting line Stress Release, make copper interconnecting line surface non-crystallization degree higher, copper atom in formed copper interconnecting line is more not easily moved, improves the time correlation dielectric breakdown of the device comprising above-mentioned copper interconnecting line.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method preventing copper from spreading in the embodiment of the present invention one;
Fig. 2 for prevent copper from spreading in the embodiment of the present invention one method handled by the cross-sectional view of copper interconnection structure;
Fig. 3 is the schematic flow sheet of the method preventing copper from spreading in the embodiment of the present invention two;
Fig. 4 for prevent copper from spreading in the embodiment of the present invention two method handled by the cross-sectional view of copper interconnection structure;
The generalized section of the copper interconnection structure that Fig. 5 is formed for the method preventing copper from spreading in the embodiment of the present invention two.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.
Set forth a lot of detail in the following description so that fully understand the present invention, but the present invention can also adopt other to be different from alternate manner described here to implement, therefore the present invention is not by the restriction of following public specific embodiment.
Just as described in the background section, hydrogen gas ionizes is become ion by high pressure by prior art, with the cupric oxide generation reduction reaction on copper interconnection structure surface, CuO is reduced into Cu, because copper atom still plays pendulum, it easily moves, at improvement and time correlation dielectric breakdown DeGrain on copper interconnection structure surface.
For the problems referred to above, inventor provide a kind of method preventing copper from spreading, comprising: Semiconductor substrate is provided, described Semiconductor substrate is formed with dielectric layer and is positioned at described dielectric layer and the copper interconnecting line that comes out of surface; By inert gas plasma, described copper interconnecting line surface is bombarded.The method that the present invention prevents copper from spreading is bombarded the copper interconnecting line surface be formed in Semiconductor substrate in dielectric layer by inert gas plasma, make the Stress Release of copper interconnecting line inside, the size of refinement copper interconnecting line internal grain, prevents copper atom generation stress migration in copper interconnecting line; In addition, by inert, plasma, bombardment is carried out to copper interconnecting line and the surface of copper interconnecting line can also be made decrystallized, copper atom is not easily moved along crystal plane direction, improves the electric property of the device comprising described copper interconnecting line.
First embodiment
With reference to figure 1, for preventing the schematic flow sheet of copper method of diffusion in the embodiment of the present invention one, said method comprising the steps of:
Step S21, provides Semiconductor substrate, described Semiconductor substrate is formed with dielectric layer and is positioned at described dielectric layer and the copper interconnecting line that comes out of surface;
Step S22, is bombarded described copper interconnecting line surface by helium gas plasma;
With reference to figure 2, for prevent copper from spreading in the embodiment of the present invention one method handled by the cross-sectional view of copper interconnection structure.In conjunction with reference to figure 1 and Fig. 2, the method preventing copper from spreading in embodiment one is described.
First, perform step S21, Semiconductor substrate 100 is provided, described Semiconductor substrate 100 is formed with dielectric layer 102 and is positioned at described dielectric layer 102 and the copper interconnecting line 104 that comes out of surface.
Concrete, the material of described Semiconductor substrate 100 is can be silicon, germanium silicon or silicon-on-insulator.In practice, described Semiconductor substrate 100 also has device layer (not shown).The such as semiconductor device such as transistor, diode is formed in described device layer.
Because extended meeting after dielectric layer 102 exists the effect of isolated copper, and copper is deep-level impurity, very high diffusion constant is had in silicon and oxide, donor level or acceptor level can be formed with alms giver or acceptor impurity in forbidden band, therefore, produce leakage current to prevent copper ion from spreading, the preferred dielectric constant (k) of material of described dielectric layer 102 is less than the advanced low-k materials of silicon dioxide (k=3.9).In concrete enforcement, the material of dielectric layer 102 can be Silicon Containing Hydrogen Barbiturates (Hydrogen Silsesquioxane, HSQ, k=2.8 ~ 3.0), containing Si-CH
3functional group contains methane-siliconic acid salt (Methylsilsesquioxane, MSQ, k=2.5 ~ 2.7), comprehensive Silicon Containing Hydrogen Barbiturates HSQ and hybrid organic siloxane polymer (the Hybrid Organic Siloxane Polymer contained synthesized by methane-siliconic acid salt MSQ, HOSP) film (k=2.5), porous SiOCH film (k=2.3 ~ 2.7), even can adopt the organic macromolecular compounds such as the porousness silicate of ultralow dielectric (k < 2.0) (Porous Silicate) and dielectric constant (k) be 1.9 porous SiOCH film.
Then, perform step S21, by helium gas plasma, described copper interconnecting line 104 surface is bombarded.
In the present embodiment, when described copper interconnecting line 104 surface being bombarded by helium gas plasma, in formation helium plasma process, the flow of helium is within the scope of 100 ~ 2000sccm, pressure is within the scope of 1 ~ 7torr, power within the scope of 100 ~ 15000W, by helium gas plasma to the bombardment time on described copper interconnecting line 104 surface within the scope of 1 ~ 20s.
In other embodiments, also helium gas plasma in step S21 can be replaced with argon plasma.When described copper interconnecting line 104 surface being bombarded by helium gas plasma, formed in argon plasma process, the flow of argon gas is within the scope of 100 ~ 2000sccm, body pressure is within the scope of 1 ~ 7torr, power within the scope of 100 ~ 15000W, by argon plasma to the bombardment time on described copper interconnecting line 104 surface within the scope of 1 ~ 20s.
In the present embodiment, by helium or argon plasma, the copper interconnecting line surface be formed in Semiconductor substrate 100 in dielectric layer 102 is bombarded, make the Stress Release of copper interconnecting line 104 inside, the size of refinement copper interconnecting line 104 internal grain, prevents copper atom generation stress migration in copper interconnecting line 104.In addition, by helium or argon plasma, bombardment is carried out to copper interconnecting line 104 and the surface of copper interconnecting line 104 can also be made decrystallized, copper atom is not easily moved along crystal plane direction, improves the electric property of the device comprising described copper interconnecting line 104.
Second embodiment
With reference to figure 3, for preventing the schematic flow sheet of copper method of diffusion in the embodiment of the present invention two, comprise the following steps:
Step S31, provides Semiconductor substrate, described Semiconductor substrate is formed with dielectric layer and is positioned at described dielectric layer and the copper interconnecting line that comes out of surface;
Step S32, is bombarded described copper interconnecting line surface by hydrogen gas plasma;
Step S33, is bombarded described copper interconnecting line surface by helium gas plasma;
Step S34, is bombarded described copper interconnecting line surface by argon plasma;
Step S35, forms the barrier layer covering described dielectric layer and copper interconnecting line surface.
With reference to figure 4 and Fig. 5, be respectively the cross-sectional view of copper interconnection structure handled by the method for preventing copper from spreading in the embodiment of the present invention two, and the generalized section of the copper interconnection structure formed after process.In conjunction with reference to figure 3 ~ Fig. 5, the method preventing copper from spreading in embodiment two is described.
First, in conjunction with reference to figure 3 and Fig. 4, perform step S31, Semiconductor substrate 200 is provided, described Semiconductor substrate 200 is formed with dielectric layer 202 and is positioned at described dielectric layer 202 and the copper interconnecting line 204 that comes out of surface.
In the present embodiment, described Semiconductor substrate 200 is identical with structure with the material of dielectric layer 102 with Semiconductor substrate 100 respectively with structure with the material of dielectric layer 202, and therefore not to repeat here.
Then, perform step S32, by hydrogen gas plasma, described copper interconnecting line 204 surface is bombarded.
In the present embodiment, when being bombarded described copper interconnecting line surface 204 by hydrogen gas plasma, the flow of hydrogen is within the scope of 100 ~ 2000sccm, and pressure is within the scope of 1 ~ 7torr, power is within the scope of 100 ~ 15000w, and bombardment time is within the scope of 1 ~ 20s.
By hydrogen gas plasma, described copper interconnecting line 204 surface is bombarded, the cupric oxide generation reduction reaction on hydrogen ion or hydrogen atom and copper interconnecting line 204 surface can be made, make copper oxide reduction be copper, prevent nonconducting cupric oxide from impacting copper interconnecting line 204 conductivity; Meanwhile, can prevent cupric oxide from impacting the adhesiveness between copper interconnecting line 204 and subsequent deposition barrier layer, improve the adhesive force between copper interconnecting line 204 and subsequent deposition barrier layer.
Again then, perform step S33, by helium gas plasma, described copper interconnecting line 204 surface is bombarded.
In the present embodiment, when described copper interconnecting line 204 surface being bombarded by helium gas plasma, formed in helium plasma process, the flow of helium is within the scope of 100 ~ 1000sccm, pressure is within the scope of 1 ~ 7torr, power within the scope of 500 ~ 1500W, by helium gas plasma to the bombardment time on described copper interconnecting line 204 surface within the scope of 10 ~ 20s.By helium gas plasma, copper interconnecting line 204 is bombarded, make the Stress Release of copper interconnecting line 204 inside, the size of refinement copper interconnecting line 204 internal grain, prevent copper atom generation stress migration in copper interconnecting line 204; In addition, by helium gas plasma, bombardment is carried out to copper interconnecting line 204 and the surface of copper interconnecting line 204 can be made decrystallized, copper atom is not easily moved along crystal plane direction, improves the electric property of the device comprising described copper interconnecting line 204.
Then, perform step S34, by argon plasma, described copper interconnecting line 204 surface is bombarded.
In the present embodiment, when described copper interconnecting line 204 surface being bombarded by argon plasma, formed in argon plasma process, the flow of argon gas is within the scope of 100 ~ 1000sccm, pressure is within the scope of 1 ~ 7torr, power within the scope of 500 ~ 1500W, by argon plasma to the bombardment time on described copper interconnecting line 204 surface within the scope of 10 ~ 20s.
Due to argon molecules, comparatively helium gas molecules is larger, after described copper interconnection layer 204 being bombarded by helium gas plasma, by argon plasma, described copper interconnecting line 204 is bombarded again, the stress of copper interconnecting line 204 inside can be made to discharge further, and make the non-crystallization degree on copper interconnecting line 204 surface higher, effective suppression copper atom moves along copper interconnecting line 204 crystal face, further increases the electric property of formed copper interconnecting line.
Finally, with reference to figure 3, perform step S35, form the barrier layer 206 covering described dielectric layer 202 and copper interconnecting line 204 surface, the generalized section of the copper interconnection structure formed as shown in Figure 5.
Concrete, the material on described barrier layer 206 is nitrogen-doped silicon carbide, and the thickness on described barrier layer is within the scope of 150 ~ 500 dusts.The formation process on described barrier layer 206 is as the known technology of those skilled in the art, and therefore not to repeat here.
Be positioned at described dielectric layer 202 and the barrier layer 206 on copper interconnecting line 204 surface that exposes can effectively prevent copper ion from copper interconnecting line 204 diffusion into the surface to other interlayer dielectric layer be positioned at above copper interconnecting line 204; In addition, described barrier layer 206 can also as etching stop layer in subsequent technique.
In the present embodiment, first by the helium plasma that molecule is less, copper interconnecting line 204 surface is bombarded, by the argon plasma that molecule is larger, copper interconnecting line 204 surface is bombarded again, while making copper interconnecting line 204 Stress Release, make the surperficial non-crystallization degree of copper interconnecting line 204 higher, copper atom in formed copper interconnecting line 204 is more not easily moved, improves the time correlation dielectric breakdown of the device comprising above-mentioned copper interconnecting line 204.
To sum up, the method that the present invention prevents copper from spreading is bombarded the copper interconnecting line surface be formed in Semiconductor substrate in dielectric layer by inert gas plasma, make the Stress Release of copper interconnecting line inside, the size of refinement copper interconnecting line internal grain, prevents copper atom generation stress migration in copper interconnecting line; In addition, by inert gas plasma, bombardment is carried out to copper interconnecting line and the surface of copper interconnecting line can also be made decrystallized, copper atom is not easily moved along crystal plane direction, improves the electric property of the device comprising described copper interconnecting line.
Although the present invention with preferred embodiment openly as above; but it is not for limiting the present invention; any those skilled in the art without departing from the spirit and scope of the present invention; the Method and Technology content of above-mentioned announcement can be utilized to make possible variation and amendment to technical solution of the present invention; therefore; every content not departing from technical solution of the present invention; the any simple modification done above embodiment according to technical spirit of the present invention, equivalent variations and modification, all belong to the protection range of technical solution of the present invention.
Claims (7)
1. the method preventing copper from spreading, is characterized in that, comprising:
Semiconductor substrate is provided, described Semiconductor substrate is formed with dielectric layer and is positioned at described dielectric layer and the copper interconnecting line that comes out of surface;
By inert gas plasma, described copper interconnecting line surface is bombarded;
Carry out bombardment by inert gas plasma to described copper interconnecting line surface to comprise: first bombarded described copper interconnecting line surface by helium gas plasma, then by argon plasma, described copper interconnecting line surface is bombarded.
2. the method preventing copper from spreading as claimed in claim 1, is characterized in that, before being bombarded described copper interconnecting line surface by inert gas plasma, also comprises: bombarded described copper interconnecting line surface by hydrogen gas plasma.
3. prevent the method that copper spreads as claimed in claim 2, it is characterized in that, when described copper interconnecting line surface being bombarded by hydrogen gas plasma, the flow of hydrogen is within the scope of 100 ~ 2000sccm, pressure is within the scope of 1 ~ 7torr, power is within the scope of 100 ~ 15000w, and the time is within the scope of 1 ~ 20s.
4. prevent the method that copper spreads as claimed in claim 1, it is characterized in that, when described copper interconnecting line surface being bombarded by helium gas plasma, the flow of helium is within the scope of 100 ~ 1000sccm, pressure is within the scope of 1 ~ 7torr, power is within the scope of 500 ~ 1500W, and the time is within the scope of 10 ~ 20s; When being bombarded described copper interconnecting line surface by argon plasma, the flow of argon gas is within the scope of 100 ~ 1000sccm, and pressure is within the scope of 1 ~ 7torr, and power is within the scope of 500 ~ 1500W, and the time is within the scope of 10 ~ 20s.
5. the method preventing copper from spreading as claimed in claim 1, is characterized in that, after being bombarded described copper interconnecting line surface by inert gas plasma, also comprises: form the barrier layer covering described dielectric layer and copper interconnecting line surface.
6. the method preventing copper from spreading as claimed in claim 5, is characterized in that, the material on described barrier layer is nitrogen-doped silicon carbide.
7. the method preventing copper from spreading as claimed in claim 5, is characterized in that, the thickness on described barrier layer is within the scope of 150 ~ 500 dusts.
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| CN101154590A (en) * | 2006-09-30 | 2008-04-02 | 中芯国际集成电路制造(上海)有限公司 | Method for preventing copper diffusion and fabricating method for semiconductor device |
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| US20110052797A1 (en) * | 2009-08-26 | 2011-03-03 | International Business Machines Corporation | Low Temperature Plasma-Free Method for the Nitridation of Copper |
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| CN101154590A (en) * | 2006-09-30 | 2008-04-02 | 中芯国际集成电路制造(上海)有限公司 | Method for preventing copper diffusion and fabricating method for semiconductor device |
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