CN1402315A - Method for reinforcing low dielectric constant material layer to resist photoresistance removing liquid damage - Google Patents
Method for reinforcing low dielectric constant material layer to resist photoresistance removing liquid damage Download PDFInfo
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- CN1402315A CN1402315A CN 01126057 CN01126057A CN1402315A CN 1402315 A CN1402315 A CN 1402315A CN 01126057 CN01126057 CN 01126057 CN 01126057 A CN01126057 A CN 01126057A CN 1402315 A CN1402315 A CN 1402315A
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Abstract
A method for increasing the resistance of low-dielectric-constant material to the damage by photoresistance removing liquid includes such steps as hydrogen-containing plasma processing on the semiconductor chip containing low-dielectric-constant material, coating photoresistance layer, generating a patterned window in the photoresistance layer, etching said low-dielectric-constant material via the window, ashing the photoresistance layer by hydrogen plasma, and immersing in the photoresistance removing liquid.
Description
Invention field
The invention provides the method for a kind of reinforcing low dielectric constant material layer opposing photo resistive removing liquor infringement, refer to a kind of method of utilizing the infringement of hydrogeneous plasma treatment (hydrogen-containing plasma treatment) reinforcing low dielectric constant material layer opposing photo resistive removing liquor especially.
Background note
Along with dwindling day by day of semiconductor element size and improving constantly of integrated circuit density, the RC late effect that is produced between incident plain conductor (RC delay effect) seriously has influence on the operational effectiveness of integrated circuit, greatly reduces the operating rate of integrated circuit.Especially drop to 0.25 micron when processing procedure live width (line width), even below 0.13 micron the time, RC late effect impact is with more obvious.
Because the influence degree that the RC late effect that is produced between metal interconnecting is caused, be directly proportional with the product mutually of the parasitic capacitance (C) of the resistance value (R) of plain conductor and the dielectric layer between plain conductor, so can utilize the lower metal of resistance value as plain conductor, or the parasitic capacitance of dielectric layer between the reduction plain conductor, to reduce the RC late effect.Aspect reduction resistance, use fine copper traditional to replace, become imperative trend with the manufacture method (multilevel metallizationprocess) of aluminium copper (Al:Cu (0.5%)) as the multi-metalization of main material as the copper tie line technology (copper interconnect technology) of conductor material.Because copper itself has lower resistivity (1.67 μ Ω-cm), and can carry higher current density and be unlikely electromigration (electromigration) problem that produces aluminium copper, therefore, can reduce the parasitic capacitance between plain conductor and the binding number of plies of plain conductor.But, only rely on copper tie line technology, the RC late effect that still can't reduce between plain conductor significantly to be produced, and copper tie line technology also exists problem on some preparation methods to wait to solve, thus utilize method that the parasitic capacitance that reduces dielectric layer between plain conductor reduces the RC late effect just order become important.
Because the parasitic capacitance of dielectric layer and the dielectric constant of dielectric layer (dielectric constant, k) relevant, so the dielectric constant of dielectric layer is low more, the parasitic capacitance that then is formed in the dielectric layer is also just relatively low more.And its dielectric constant of traditional silicon dioxide is 3.9, gradually, can't satisfy the demand of present semiconductor fabrication below 0.13 micron, so advanced low-k materials that some are new, polyimides (polyimide for example, PI), material such as PLARETM, FPI, PAE-2, PAE-3 or LOSP, proposed successively in recent years.Though yet these advanced low-k materials have the low dielectric constant values between 2.6～3.2, but these general principal components are the dielectric materials of hydrocarbon oxygen, still be the aspects such as every character of itself no matter in adhesive force, etch effect with other materials, all notable difference is arranged with traditional silicon dioxide, and wherein major part has shortcomings such as the not good and thermal stability deficiency of tack, therefore still can't properly be integrated at present general IC manufacture process commonly used.
Therefore, some are that some hydrocarbon inorganic dielectric layer with low dielectric constant that wait element are mixed on the basis then again with silicon dioxide in material, for example dielectric constant values is that 2.8 HSQ (hydrogensilsesquioxane), dielectric constant values are that 2.7 MSQ (methyl silsesquioxane) and dielectric constant values are 2.5 materials such as HOSP, because its character and traditional silicon dioxide are more or less the same, therefore the semiconductor fabrication process of knowing at present there is higher integration ability, and by had an optimistic view of in the future.
Please refer to Fig. 1 to Fig. 3, Fig. 1 to Fig. 3 is the schematic diagram of the removal photoresistance method known.As shown in Figure 1, semiconductor wafer 10 surfaces comprise silicon base 12, and utilize chemical vapour deposition technique or spin coating mode (spin-on) to be formed at surface on the silicon base 12, be that the material of basic structure constitutes low dielectric constant material layer 14 with silicon dioxide by HSQ, MSQ or HOSP etc.
As shown in Figure 2, at first on low dielectric constant material layer 14, be coated with photoresist layer 16, and in photoresist layer 16, form pattern openings 18, to expose the low dielectric constant material layer 14 of part.Subsequently via pattern openings 18 dry ecthing low dielectric constant material layers 14, with the design transfer in the photoresist layer 16 to low dielectric constant material layer 14.
Afterwards as shown in Figure 3, carry out the removing photoresistance manufacture process, utilize oxygen gas plasma ashing photoresist layer 16 earlier, make the carbon in oxygen plasma and the photoresist layer 16, carbon dioxide and the water vapour that the protium complete reaction forms gaseous state.At last with ACT-935 as photo resistive removing liquor, in order to soak (dipping) semiconductor wafer 10, remove photoresist layer 16 fully.
Yet, to by for example HSQ, MSQ or HOSP etc. being dielectric layer that the inorganic advanced low-k materials of basic structure constitutes when carrying out design transfer,, all can damage dielectric layer no matter at etching dielectric layer or carry out in the process of removing photoresistance with silicon dioxide.The blocking solution of delustering removes photoresistance because the removing photoresistance process is used dry type oxygen plasma ashing (ashing) method and wet type usually simultaneously, so make the bond on dielectric layer surface be interrupted by oxygen plasma easily, and react with the blocking solution of delustering of alkalescence, make impaired dielectric layer surface form the Si-OH key of absorption aqueous vapor easily.Because the dielectric constant values of water is up to 78, therefore after the absorption aqueous vapor, the dielectric constant of dielectric layer and leakage current all can rise significantly, even the generation of the situation of the toxic interlayer hole of meeting (poison via), have a strong impact on the reliability of product.
Summary of the invention
Therefore, main purpose of the present invention is to provide the method for a kind of reinforcing low dielectric constant material layer opposing photo resistive removing liquor infringement, the problem that significantly rises with the dielectric constant that solves dielectric layer with low dielectric constant in the above-mentioned well-known process and leakage current.
In most preferred embodiment of the present invention, comprise a low dielectric constant material layer on the semiconductor wafer.At first utilize hydrogen plasma (hydrogen plasma), carry out the first hydrogeneous plasma treatment step, the ability that corrodes with the surperficial anti-photo resistive removing liquor of strengthening this low dielectric constant material layer.Then on this low dielectric constant material layer, be coated with photoresist layer, and in this photoresist layer, form pattern openings, to expose this low dielectric constant material layer of part.Afterwards via this this low dielectric constant material layer of pattern openings dry ecthing, with the design transfer in this photoresist layer to this low dielectric constant material layer, utilize this photoresist layer of oxygen gas plasma ashing again.Then carry out the second hydrogeneous plasma treatment step, the ability that corrodes with the surperficial anti-photo resistive removing liquor of further strengthening this low dielectric constant material layer.Soak this semiconductor wafer at last in photo resistive removing liquor, to remove this photoresist layer fully.
Because manufacture method of the present invention is before carrying out etching process, dielectric layer at low-k carries out hydrogeneous plasma treatment earlier, form a passivation layer with dielectric layer surface in low-k, therefore when follow-up removing photoresistance process of carrying out, can reduce oxygen plasma contacts with the dielectric layer of low-k with the blocking solution of delustering, avoid the dielectric layer of low-k to come to harm, and prevent that effectively the Si-OH key is formed in the dielectric layer of low-k simultaneously, thoroughly solve the dielectric constant of the dielectric layer with low dielectric constant of knowing that the preparation method caused and the problem that leakage current all significantly increases.
Detailed description of the invention
Please refer to Fig. 4 to Fig. 8, Fig. 4 to Fig. 8 is the schematic diagram of reinforcing low dielectric constant material layer opposing photo resistive removing liquor infringement method of the present invention.As shown in Figure 4, semiconductor wafer 40 comprises silicon base 42, and utilize chemical vapour deposition technique or spin coating mode to be formed at surface on the silicon base 42, being respectively 2.8,2.7 and 2.5 HSQ, MSQ or HOSP etc. by dielectric constant is the material layer 44 that the material of basic structure constitutes low-k with silicon dioxide.
As shown in Figure 5, at first utilize under the pressure of 200 to 350 ℃ temperature and 200 to 350 millitorrs (mTorr), relying on flow is the hydrogen of 200 to 350 standard cubic centimeter per minutes, cooperate 90 to 150 watts of formed hydrogen plasmas that contain of wireless power, carry out the first hydrogeneous plasma treatment step 46 and reach more than 1 minute.Because the dielectric layer 44 of low-k contains silicon, oxygen atom, therefore the surface of dielectric layer with low dielectric constant 44 can contain hydrogen plasma with this and reacts, form passivation layer 48, the ability that corrodes with the anti-photo resistive removing liquor on reinforcing low dielectric constant material layer 44 surfaces, prevent that effectively aqueous vapor is adsorbed in the surface of dielectric layer with low dielectric constant 44, and can be used as the barrier layer that suppresses the copper diffusion.
Then as shown in Figure 6, coating photoresist layer 50 on low dielectric constant material layer 44 forms pattern openings 52, again to expose the low dielectric constant material layer 44 of part in photoresist layer 50.Subsequently as shown in Figure 7, via pattern openings 52 dry ecthing low dielectric constant material layers 44, with the design transfer in the photoresist layer 50 to low dielectric constant material layer 44.
As shown in Figure 8, carry out the removing photoresistance process, utilize oxygen gas plasma ashing photoresist layer 50 earlier, make the carbon in oxygen plasma and the photoresist layer 50, carbon dioxide and the water vapour that the protium complete reaction forms gaseous state, carry out the second hydrogeneous plasma treatment step again, the ability that corrodes with the anti-photo resistive removing liquor on further reinforcing low dielectric constant material layer 44 surfaces.At last, as photo resistive removing liquor,, remove photoresist layer 50 fully with ACT-935 in order to soak semiconductor wafer 40.Because dielectric layer with low dielectric constant 44 surfaces have passivation layer 48, therefore, dielectric layer with low dielectric constant 44 is not easy in this removing photoresistance process impaired and the Si-OH key of aqueous vapor is adsorbed in the formation meeting in a large number, so can avoid the rising significantly of the dielectric constant and the leakage current of dielectric layer with low dielectric constant 44 effectively.
Please refer to Fig. 9, Fig. 9 is HSQ resulting infrared spectrum under the different hydro plasma treatment time.As shown in Figure 9, on behalf of the HSQ dielectric layer of handling without the inventive method, curve A, B carrying out the forward and backward infrared spectrum of removing photoresistance process respectively, curve C, D, E then utilize the inventive method earlier for the HSQ dielectric layer, carry out 3,6,9 minutes hydrogeneous plasma treatment respectively, carry out removing photoresistance process resulting infrared spectrum afterwards again.Wherein, absworption peak 1 and absworption peak 2 are represented the absworption peak of Si-H and Si-OH key respectively, and it absorbs position and lays respectively at 2200 to 2300cm
-1And 3000 to 3500cm
-1Wave-number range in.
Tranmittance than curve A, B as can be known, the HSQ dielectric layer is after process removing photoresistance process, the absworption peak 1 that originally is arranged in the Si-H key of HSQ dielectric layer disappears, and non-existent Si-OH key absworption peak 2 originally appears, prove that containing hydrogen plasma and the wet type blocking solution of delustering obviously causes the dielectric layer surface texture impaired.And by curve C, D, E as can be known, the absworption peak 1 through the HSQ of hydrogeneous plasma treatment dielectric layer still exists earlier, and can not produce absworption peak 2, and hydrogeneous plasma treatment step can prevent successfully that the Si-H key from being interrupted, and reaches the purpose of avoiding forming the Si-OH key.In addition, the trap of the absworption peak 1 of Si-H key descends with the increase of hydrogeneous plasma treatment time significantly, be controlled within 20 minutes so carry out the time suggestion of plasma treatment, impaired to avoid making on the dielectric layer Si-H functional group because of the processing time is long.
Please refer to Figure 10 and Figure 11, Figure 10 and Figure 11 show the influence of hydrogeneous plasma treatment time to the dielectric constant and the leakage current of HSQ dielectric layer respectively.As shown in figure 10, carry out hydrogeneous plasma treatment step and reach 3,6,9 minutes HSQ dielectric layer, its dielectric constant all is lower than the dielectric constant without the HSQ dielectric layer of hydrogeneous plasma treatment step, and carrying out after hydrogeneous plasma treatment step surpasses 3 minutes, the dielectric constant of HSQ dielectric layer can maintain about 3, does not influence the value of dielectric constant so increase the time of hydrogeneous plasma treatment.As shown in figure 11, square ■, equilateral triangle ▲, del represents respectively through after 3,6,9 minutes the hydrogeneous plasma treatment, carry out again in the HSQ dielectric layer of removing photoresistance process, the relation curve of electric field and leakage current, and circular ● then represent without hydrogeneous plasma treatment and just carry out in the HSQ dielectric layer of removing photoresistance process, the relation curve of electric field and leakage current.As shown in figure 11, with respect to dielectric layer without hydrogeneous plasma treatment step, earlier the leakage current through the HSQ of hydrogeneous plasma treatment dielectric layer can significantly reduce by 2 to 3 progression, and the time that increases hydrogeneous plasma treatment also can obviously not influence the size of leakage current.So in most preferred embodiment of the present invention, the time of carrying out hydrogeneous plasma treatment is about 3 minutes.
With respect to the technology of knowing, the present invention carried out hydrogeneous plasma treatment to dielectric layer with low dielectric constant 44 earlier before carrying out etching process, to form passivation layer 48 on dielectric layer with low dielectric constant 44 surfaces, therefore, in follow-up removing photoresistance process of carrying out, can reduce oxygen plasma and the contacting of deluster blocking solution and dielectric layer with low dielectric constant 44, and then avoid dielectric layer with low dielectric constant 44 to come to harm.In addition, method of the present invention can prevent effectively that also the Si-OH key is formed in the dielectric layer with low dielectric constant 44, so can solve the dielectric constant of dielectric layer with low dielectric constant that known preparation method causes and the problem that leakage current all increases considerably.
The above only is preferred embodiment of the present invention, and all equalizations of being done according to claim scope of the present invention change and modify, and all belong to protection scope of the present invention.
Illustrated simple declaration
Fig. 1 to Fig. 3 is the schematic diagram of known removal photoresistance method.
Fig. 4 to Fig. 8 is the schematic diagram of the method for reinforcing low dielectric constant material layer opposing photo resistive removing liquor of the present invention infringement.
Fig. 9 is HSQ resulting infrared spectrum under the different hydro plasma treatment time.
Figure 10 is the influence of hydrogeneous plasma treatment time to the dielectric constant of HSQ dielectric layer.
Figure 11 is the influence of hydrogeneous plasma treatment time to the leakage current of HSQ dielectric layer.
Illustrated symbol description
10 semiconductor wafers, 12 silicon base
14 low dielectric constant material layers, 16 photoresist layers
18 pattern openings, 40 semiconductor wafers
42 silicon base, 44 low dielectric constant material layers
46 first hydrogeneous plasma treatment steps
48 passivation layers, 50 photoresist layers
52 pattern openings
Claims (20)
1. a reinforcing low dielectric constant material layer is resisted the method that photo resistive removing liquor (stripper) damages, and this method comprises the following steps:
Semiconductor wafer is provided, comprises a low dielectric constant material layer on it;
Carry out the first hydrogeneous plasma treatment step, the ability that corrodes with the opposing photo resistive removing liquor of strengthening this low dielectric constant material layer surface;
On this low dielectric constant material layer, be coated with photoresist layer;
In this photoresist layer, form pattern openings, to expose this low dielectric constant material layer of part;
Via this this low dielectric constant material layer of pattern openings dry ecthing, with the design transfer in this photoresist layer to this low dielectric constant material layer;
Utilize this photoresist layer of oxygen gas plasma ashing; And
Soak this semiconductor wafer in photo resistive removing liquor, to remove this photoresist layer fully.
2. the method for claim 1, wherein this low dielectric constant material layer is the low dielectric constant material layer of silicon-dioxide-substrate.
3. the method for claim 1, wherein this low dielectric constant material layer is made of one of following material: HSQ, MSQ or HOSP.
4. the method for claim 1, wherein this first hydrogeneous plasma treatment step has used hydrogen plasma.
5. method as claimed in claim 4, the wireless power that wherein forms this hydrogen plasma are 90 to 150 watts.
6. method as claimed in claim 4, the hydrogen flowing quantity that wherein forms this hydrogen plasma are 200 to 350 standard cubic centimeter per minutes.
7. method as claimed in claim 4, the temperature that wherein forms this hydrogen plasma are 200 to 350 ℃.
8. method as claimed in claim 4, the pressure that wherein forms this hydrogen plasma are 200 to 350 millitorrs.
9. the method for claim 1, wherein this first hydrogeneous plasma treatment step need carry out more than 1 minute at least.
10. the method for claim 1, wherein this photo resistive removing liquor is ACT-935.
11. the method for claim 1, wherein after with this this photoresist layer of oxygen gas plasma ashing, and before removing this photoresist layer fully with this photo resistive removing liquor, this method also comprises: carry out the second hydrogeneous plasma treatment step, the ability that corrodes with the anti-photo resistive removing liquor on this low dielectric constant material layer surface of further reinforcement.
12. a method of strengthening the infringement of silicon-dioxide-substrate low dielectric constant material layer opposing photo resistive removing liquor, this method comprises the following steps:
Semiconductor wafer is provided, includes a low dielectric constant material layer on it;
On this low dielectric constant material layer, be coated with photoresist layer;
In this photoresist layer, form pattern openings, to expose this low dielectric constant material layer of part;
Via this this low dielectric constant material layer of pattern openings dry ecthing, with the design transfer in this photoresist layer to this low dielectric constant material layer;
Utilize this photoresist layer of oxygen gas plasma ashing;
Soak this semiconductor wafer in photo resistive removing liquor, to remove this photoresist layer fully; And
Carry out carrying out once hydrogeneous plasma treatment at least before photo resistive removing liquor soaks the ability that corrodes with the anti-photo resistive removing liquor of strengthening this low dielectric constant material layer surface at this semiconductor wafer.
13. method as claimed in claim 12, wherein this silicon-dioxide-substrate low dielectric constant material layer is made of one of following material: HSQ, MSQ or HOSP.
14. method as claimed in claim 12, wherein this hydrogeneous plasma treatment step has used hydrogen plasma.
15. method as claimed in claim 14, the wireless power that wherein forms this hydrogen plasma are 90 to 150 watts.
16. method as claimed in claim 14, the hydrogen flowing quantity that wherein forms this hydrogen plasma are 200 to 350 standard cubic centimeter per minutes.
17. method as claimed in claim 14, the temperature that wherein forms this hydrogen plasma are 200 to 350 ℃.
18. method as claimed in claim 14, the pressure that wherein forms this hydrogen plasma are 200 to 350 millitorrs.
19. method as claimed in claim 12, wherein this photo resistive removing liquor is ACT-935.
20. method as claimed in claim 12, wherein this hydrogeneous plasma treatment step carried out before this photoresist layer of coating.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 01126057 CN1402315A (en) | 2001-08-28 | 2001-08-28 | Method for reinforcing low dielectric constant material layer to resist photoresistance removing liquid damage |
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| CN 01126057 CN1402315A (en) | 2001-08-28 | 2001-08-28 | Method for reinforcing low dielectric constant material layer to resist photoresistance removing liquid damage |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320609C (en) * | 2003-10-23 | 2007-06-06 | 台湾积体电路制造股份有限公司 | Semiconductor device and forming method thereof |
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- 2001-08-28 CN CN 01126057 patent/CN1402315A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320609C (en) * | 2003-10-23 | 2007-06-06 | 台湾积体电路制造股份有限公司 | Semiconductor device and forming method thereof |
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