CN101515580B - SiCN medium diffusion barrier film for copper interconnection and preparation process thereof - Google Patents
SiCN medium diffusion barrier film for copper interconnection and preparation process thereof Download PDFInfo
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- CN101515580B CN101515580B CN2009100430009A CN200910043000A CN101515580B CN 101515580 B CN101515580 B CN 101515580B CN 2009100430009 A CN2009100430009 A CN 2009100430009A CN 200910043000 A CN200910043000 A CN 200910043000A CN 101515580 B CN101515580 B CN 101515580B
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Abstract
The invention discloses a SiCN medium diffusion barrier film for copper interconnection. The film is characterized by being prepared from the raw materials comprising 10%-15% of N, 15%-20% of C and Si in mass percentage by a magnetron sputtering method. The invention further discloses a process for preparing the SiCN medium diffusion barrier film, and the specific method is a reaction magnetron sputtering method. The barrier property of the SiCN film fails after being annealed at the temperature of 600 DEG C for 5min. Compared with the traditional Si3N4 barrier, the SiCN barrier film has high-efficiency barrier property and good adhesivity to a Si substrate; and can obviously reduce RC delay due to lower dielectric constant, thus facilitating to enhance device performance.
Description
Technical field
The present invention relates to a kind of diffusion impervious layer SiCN film and technology of preparing thereof that is applied to integrated circuit preparation technology, especially a kind of SiCN medium diffusion barrier film and preparation technology thereof who is used for copper-connection.
Background technology
Along with the development of very lagre scale integrated circuit (VLSIC), the RC of the metal interconnected system of integrated circuit postpones and crosstalks just to replace the principal element that gate delay becomes the further raising of restriction integrated circuit speed.Adopt the Cu/ low-K dielectric to replace traditional Al/SiO
2System can make performance of integrated circuits significantly improve.Yet because that Cu spreads in Si and oxide and most of medium is quite fast, and in a single day Cu get into and promptly form deep-level impurity in the device architecture, and the charge carrier in the device is had very strong trap effect, makes device performance degeneration even inefficacy.Therefore must between Cu and dielectric layer, increase a diffusion impervious layer, stop the diffusion of Cu.The barrier layer requires that good thermal stability is arranged, and with Cu and dielectric layer good combination is arranged.
Dielectric impedance material commonly used comprises silica (SiO
x), silicon nitride (SiN
x), SiO
xN
y, SiOF, Al
2O
3Or the like.Traditionally, in the semiconductor integrated circuit manufacturing, use SiO
2Prevent that with similar oxide interconnecting metal thermal diffusion or electric field driven in the device from spreading the device early failure that is caused, yet the barrier effect of these materials is relatively poor, SiO
xN
yAs the barrier layer, just begin have Cu to diffuse into device architecture after 450 ℃ of thermal stress.So, adopted more excellent amorphous hydrogenated silicon nitride (a-SiN:H) the material substitution SiO of barrier properties in the prior art
2Deng material.Yet,, require metal interconnected RC to postpone and will further reduce in the industry, because above-mentioned nitride or oxide have the SiO of being equal to or higher than along with further dwindling of integrated circuit characteristic size
2Dielectric constant, cause dielectric capacitance to increase, so these materials are challenged.
Summary of the invention
The object of the present invention is to provide SiCN medium diffusion barrier film and preparation technology thereof in a kind of copper-connection; To stop that the Cu atom spreads to inter-level dielectric; Improve the high-temperature stability of medium diffusion barrier, reduce inter-level dielectric electric capacity simultaneously, reduce RC and postpone.
For realizing above-mentioned purpose, technical scheme of the present invention is:
A kind of SiCN medium diffusion barrier film that is used for copper-connection is characterized in that this film is comprising that mass percent is that the raw material that 10%～15% N, 15%～20% C and surplus are Si is prepared from through magnetically controlled sputter method.
The described relative dielectric constant that is used for the SiCN medium diffusion barrier film of copper-connection is 4.8～4.2.
The described SiCN medium diffusion barrier film that is used for copper-connection is a noncrystalline membrane.
In addition; The present invention also provides a kind of preparation technology who is used for the SiCN medium diffusion barrier film of copper-connection; This constituent mass ratio that is used for the SiCN medium diffusion barrier film of copper-connection is: N content is 10～15%, and C content is 15～20%, and all the other are Si; This preparation technology may further comprise the steps:
1) SiC target, Cu target are installed simultaneously in the multi-target magnetic control sputtering appearance; Wherein the Cu target is in the direct current sputtering position, and the SiC target is in the radio frequency sputtering position, with being installed on the substrate position behind the silicon chip cleaning, drying; Charge into air-flow, nitrogen accounts for 20～50% of air-flow total flow in the control air-flow;
2) adopt magnetron sputtering method in-situ preparing SiCN film;
3) direct current sputtering copper film on the SiCN film.
Described a kind of preparation is used for the technology of the SiCN medium diffusion barrier film of copper-connection, and during magnetron sputtering, the SiC target adopts radio-frequency power supply, and its radio-frequency power is 100～300 watts, preferred 150 watts.
When preparing the SiCN film in position, with the stable gas pressure of air-flow at 0.8～1.0Pa.
As improvement, when preparing the SiCN film in position, silicon chip is rotated to improve into film uniformity.
Described this preparation is used for the technology of the SiCN medium diffusion barrier film of copper-connection, and its characteristic is that also silicon chip is cleaned described in the step 1) is: with deionized water, ultrasonic wave, absolute ethyl alcohol and or acetone silicon chip is cleaned.In step 3), copper film thickness is at 150～200nm, preferred 50～100nm.
SiCN medium diffusion barrier film of the present invention, dense structure, good with matrix bond, its constituent mass score is: N content is 10～15%, and C content is 15～20%, and all the other are Si.
Beneficial effect of the present invention is following:
Described SiCN film and traditional Si among the present invention
3N
4Dielectric barrier is compared, and when keeping the good adhesion of Si base barrier material, because the high-temperature-resistant and anti-corrosion property of this new material, can under 600 ℃ or higher technological temperature, effectively stop the diffusion of Cu.After 5 minutes, its diffusion barrier property just lost efficacy the SiCN film that the present invention obtains, and obviously was superior to common SiN through 600 ℃ of annealing
xThe barrier layer.Because described SiCN thin film growth process is nonequilibrium state, the film that obtains is an amorphous, and this structure can significantly reduce faults of construction such as crystal boundary, has reduced the express passway that Cu spreads therein, thereby improves barrier properties.This film also can impel copper along (111) oriented growth simultaneously; (111) the deelectric transferred ability of Cu film of orientation is better than other growth orientation; Therefore to help improving the Cu film deelectric transferred for SiCN medium diffusion barrier film of the present invention, thereby improve the reliability of device.
Barrier film of the present invention can be through the magnetron sputtering method preparation, with traditional Si
3N
4The barrier layer is compared, and SiCN film of the present invention is when having kept the good adhesion of Si base barrier material, because the high-temperature-resistant and anti-corrosion property of this new material can effectively improve its barrier properties; In addition, the relative dielectric constant (being 4.8～4.2) of the SiCN film that obtains of the present invention is less than Si
3N
4Relative dielectric constant (being about 7) because lower dielectric constant can effectively reduce dielectric capacitance, postpone thereby can obviously reduce RC, reach the purpose that improves device performance.
Therefore SiCN medium diffusion barrier film of the present invention is a kind of excellent performance, and the diffusion impervious layer of application prospect is arranged, and its preparation technology is a kind of barrier technology that has prospect.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explain.
Embodiment 1
Adopt TXZ500-I type magnetron sputtering coater to deposit the SiCN medium diffusion barrier film that is used for copper-connection with radio frequency sputtering, direct current sputtering mode.This preparation technology comprises: SiC target, Cu target are installed in this multi-target magnetic control sputtering appearance simultaneously; Described target is the sintered sic target of diameter 100mm and the Cu target of diameter 100mm; Wherein said Cu target is in the direct current sputtering position; Described SiC target is in the radio frequency sputtering position, and the distance of target position and substrate position is 6cm.With the monocrystalline silicon piece is substrate, uses the 5%HF rinsing earlier, to remove surface oxide layer.Carry out ultrasonic cleaning with deionized water, acetone, absolute alcohol then, each scavenging period is 15min, washes repeatedly with deionized water at last.With being installed on the substrate position behind the described silicon chip cleaning, drying.During sputter, earlier vacuum is evacuated to 1.0 * 10 in advance
-3Pa feeds high-purity sputter gas Ar (purity>=99.99%) to the preparatory sputter 2min of substrate, to remove the substrate surface adsorbate, simultaneously the gas that adsorbs on the substrate to remove is toasted in substrate.Charge into high-purity Ar and N then
2(purity>=99.99%) air-flow, control nitrogen accounts for 50% of air-flow total flow, adopts reactive sputtering in-situ deposition SiCN film.During magnetron sputtering, with substrate rotation improving into film uniformity, and with the stable gas pressure of working air current in the vacuum chamber at 0.8Pa, the SiC target adopts radio-frequency power supply, its radio-frequency power is 150 watts.Direct current sputtering copper film on described SiCN film at last, during sputter, the stable gas pressure of working air current is at 0.88Pa in the vacuum chamber, and the Cu target adopts DC power supply, and its radio-frequency power is 200 watts.All flow processs of film preparation are all accomplished in 1000 grades ultra-clean chamber.
The SiCN film thickness of preparation is 50nm; Be noncrystal membrane; Its constituent mass score is: N content is 15%, and C content is 15%, and all the other are Si; The relative dielectric constant of this SiCN diffusion barrier film is 4.8.The Cu film thickness of preparation is 100nm.After 5 minutes, Cu diffusion therein is not obvious, has excellent barrier properties 600 ℃ of annealing for this film.
Embodiment 2
Adopt TXZ500-I type magnetron sputtering coater to deposit the SiCN medium diffusion barrier film that is used for copper-connection with radio frequency sputtering, direct current sputtering mode.This preparation technology comprises: SiC target, Cu target are installed in this multi-target magnetic control sputtering appearance simultaneously; Described target is the sintered sic target of diameter 100mm and the Cu target of diameter 100mm; Wherein said Cu target is in the direct current sputtering position; Described SiC target is in the radio frequency sputtering position, and the distance of target position and substrate position is 6cm.With the monocrystalline silicon piece is substrate, uses the 5%HF rinsing earlier, to remove surface oxide layer.Carry out ultrasonic cleaning with deionized water, acetone, absolute alcohol then, each scavenging period is 15min, washes repeatedly with deionized water at last.With described silicon chip clean dry by the fire in after be installed on the substrate position.During sputter, earlier vacuum is evacuated to 1.0 * 10 in advance
-3Pa feeds high-purity sputter gas Ar (purity>=99.99%) to the preparatory sputter 2min of substrate, to remove the substrate surface adsorbate, simultaneously the gas that adsorbs on the substrate to remove is toasted in substrate.Charge into high-purity Ar and N then
2(purity>=99.99%) air-flow, control nitrogen accounts for 30% of air-flow total flow, adopts reactive sputtering in-situ deposition SiCN film.During magnetron sputtering, with substrate rotation improving into film uniformity, and with the stable gas pressure of working air current in the vacuum chamber at 0.8Pa, the SiC target adopts radio-frequency power supply, its radio-frequency power is 200 watts.Direct current sputtering copper film on described SiCN film at last, during sputter, the stable gas pressure of working air current is at 0.88Pa in the vacuum chamber, and the Cu target adopts DC power supply, and its radio-frequency power is 200 watts.All flow processs of film preparation are all accomplished in 1000 grades ultra-clean chamber.
The SiCN film thickness of preparation is 50nm; Be noncrystal membrane; Its constituent mass score is: N content is 12%, and C content is 18%, and all the other are Si; The relative dielectric constant of this SiCN diffusion barrier film is 4.5.The Cu film thickness of preparation is 80nm.After 5 minutes, Cu diffusion therein is still not obvious, can effectively stop the diffusion of Cu 600 ℃ of annealing for this film.
Embodiment 3
Adopt TXZ500-I type magnetron sputtering coater to deposit the SiCN medium diffusion barrier film that is used for copper-connection with radio frequency sputtering, direct current sputtering mode.This preparation technology comprises: SiC target, Cu target are installed in this multi-target magnetic control sputtering appearance simultaneously; Described target is the sintered sic target of diameter 100mm and the Cu target of diameter 100mm; Wherein said Cu target is in the direct current sputtering position; Described SiC target is in the radio frequency sputtering position, and the distance of target position and substrate position is 6cm.With the monocrystalline silicon piece is substrate, uses the 5%HF rinsing earlier, to remove surface oxide layer.Carry out ultrasonic cleaning with deionized water, acetone, absolute alcohol then, each scavenging period is 15min, washes repeatedly with deionized water at last.With being installed on the substrate position behind the described silicon chip cleaning, drying.During sputter, earlier vacuum is evacuated to 1.0 * 10 in advance
-3Pa feeds high-purity sputter gas Ar (purity>=99.99%) to the preparatory sputter 2min of substrate, to remove the substrate surface adsorbate, simultaneously the gas that adsorbs on the substrate to remove is toasted in substrate.Charge into high-purity Ar and N then
2(purity>=99.99%) air-flow, control nitrogen accounts for 20% of air-flow total flow, adopts reactive sputtering in-situ deposition SiCN film.During magnetron sputtering, with substrate rotation improving into film uniformity, and with the stable gas pressure of working air current in the vacuum chamber at 0.8Pa, the SiC target adopts radio-frequency power supply, its radio-frequency power is 150 watts.Direct current sputtering copper film on described SiCN film at last, during sputter, the stable gas pressure of working air current is at 0.88Pa in the vacuum chamber, and the Cu target adopts DC power supply, and its radio-frequency power is 200 watts.All flow processs of film preparation are all accomplished in 1000 grades ultra-clean chamber.
The SiCN film thickness of preparation is 50nm; Be noncrystal membrane; Its constituent mass score is: N content is 10%, and C content is 20%, and all the other are Si; The relative dielectric constant of this SiCN diffusion barrier film is 4.2.The Cu film thickness of preparation is 50nm.This film is 600 ℃ of annealing after 5 minutes, Cu therein diffusion arranged, but the diffusion of Cu still can effectively stop the diffusion of Cu still through this diffusion impervious layer.
Claims (7)
1. SiCN medium diffusion barrier film that is used for copper-connection; It is characterized in that: comprising that mass percent is that the raw material that 10%～15% N, 15%～20% C and surplus are Si is prepared from through magnetically controlled sputter method, this SiCN medium diffusion barrier film that is used for copper-connection is an amorphous state.
2. the SiCN medium diffusion barrier film that is used for copper-connection as claimed in claim 1 is characterized in that: this relative dielectric constant that is used for the SiCN medium diffusion barrier film of copper-connection is 4.8～4.2.
3. preparation technology who is used for the SiCN medium diffusion barrier film of copper-connection according to claim 1 is characterized in that this preparation technology may further comprise the steps:
1) SiC target and Cu target are installed in the multi-target magnetic control sputtering appearance; Wherein the Cu target is in the direct current sputtering position, and the SiC target is in the radio frequency sputtering position, with being installed on the substrate position behind the silicon chip cleaning, drying; Charge into air-flow, nitrogen accounts for 20～50% of air-flow total flow in the control air-flow;
2) adopt magnetron sputtering method in-situ preparing SiCN film;
3) direct current sputtering copper film on the SiCN film.
4. a kind of preparation as claimed in claim 3 is used for the technology of the SiCN medium diffusion barrier film of copper-connection, it is characterized in that: the SiC target adopts radio-frequency power supply during magnetron sputtering, and radio-frequency power is 100～300 watts.
5. a kind of preparation as claimed in claim 3 is used for the technology of the SiCN medium diffusion barrier film of copper-connection, it is characterized in that, when preparing the SiCN film in position, with the stable gas pressure of air-flow at 0.8～1.0Pa.
6. a kind of preparation as claimed in claim 3 is used for the technology of the SiCN medium diffusion barrier film of copper-connection, it is characterized in that, in step 3), copper film thickness is at 50～100nm.
7. each described a kind of preparation is used for the technology of the SiCN medium diffusion barrier film of copper-connection like claim 3～6, it is characterized in that, when preparing the SiCN film in position, silicon chip is rotated.
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| CN2009100430009A CN101515580B (en) | 2009-03-31 | 2009-03-31 | SiCN medium diffusion barrier film for copper interconnection and preparation process thereof |
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|---|---|---|---|
| CN2009100430009A CN101515580B (en) | 2009-03-31 | 2009-03-31 | SiCN medium diffusion barrier film for copper interconnection and preparation process thereof |
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| CN101515580B true CN101515580B (en) | 2012-07-25 |
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| CN102002666B (en) * | 2010-10-22 | 2012-06-27 | 哈尔滨工业大学 | Preparation method of tantalum nitride diffusion impervious layer for copper interconnection |
| JP6128935B2 (en) * | 2012-05-22 | 2017-05-17 | キヤノン株式会社 | Substrate for liquid discharge head and liquid discharge head |
| CN106591791A (en) * | 2016-12-30 | 2017-04-26 | 西北大学 | Preparation method for SiCN thin film |
| CN108330460A (en) * | 2018-03-19 | 2018-07-27 | 西北大学 | A kind of SiCN films heat treatment method |
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