CN103956331B - A kind of thin film for porous connected medium surface-sealing and preparation method thereof - Google Patents
A kind of thin film for porous connected medium surface-sealing and preparation method thereof Download PDFInfo
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- CN103956331B CN103956331B CN201410175490.9A CN201410175490A CN103956331B CN 103956331 B CN103956331 B CN 103956331B CN 201410175490 A CN201410175490 A CN 201410175490A CN 103956331 B CN103956331 B CN 103956331B
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Abstract
The invention belongs to super large-scale integration manufacturing technology field, a kind of preparation method for porous connected medium surface-sealing material.The present invention as liquid source, enters cavity and C with helium (He) carrier gas with organic liquid source triethoxy methyl silicane (MTES) after overflash2F6Gas mixes, and using plasma strengthens chemical gaseous phase deposition (PECVD) technique, deposits thin film on porous low dielectric constant connected medium surface.The dielectric constant of this thin film is 2.8 3.3, and under the electric field intensity of 1MV/cm, leakage current density is 10‑9A/cm2The order of magnitude, Young's modulus is 16.21 37.33 GPa, and hardness is 1.25 3.03 GPa.This material film, in super large-scale integration rear end interconnects, can be used for the sealing of hole of porous connected medium layer, simultaneously works as strengthening the adhesion strength between porous medium layer and cap or diffusion impervious layer.
Description
Technical field
The invention belongs to super large-scale integration manufacturing technology field, be specifically related to a kind of for porous connected medium table
Thin film of face sealing of hole and preparation method thereof.
Background technology
Due to the extensive development of integrated circuit, its characteristic size reduces the most rapidly, has thus resulted in integrated circuit
Interconnection RC(R refers to that resistance, C refer to electric capacity) being increased dramatically of postponing, strongly limit the speed that circuit runs, and bring train of signal
The problem disturbed and increase power consumption.Replace aluminum that integrated circuit resistor can be made to decline with copper；Equally, reducing parasitic capacitance is also to improve collection
Become the effective way of circuit performance, wherein, replace SiO with low-k (k) material2(k ≈ 4.0) is effective method
[1].In order to obtain the thin-film material of lower k-values, having two kinds of effective approach, one is introducing hole in thin-film material, with
The increase of porosity, k value just reduces；Another kind is to introduce Si-C key, Si-F key and the C-C key that polarity is less in the film
[2,3].Additionally, in low k films material integrated circuit to be applied to, it is necessary to its heat stability, hydrophobicity, electrical property will be considered
Energy and mechanical strength etc. [4,5,6].
The preparation method of low-k materials thin film mainly includes spin coating and plasma enhanced chemical vapor deposition (PECVD) skill
Art.Utilize PECVD technique, organic liquid source mix pore former and can effectively reduce dielectric constant, but its mechanical property and
Electric property can decline.On the other hand, owing to ultralow-k material film has high porosity, itself and cap therefore can be caused
Adhesion declines, or more cap material enters into and causes effective dielectric of connected medium layer in the hole of ultralow-k material film
Constant raises.In order to solve high porosity dielectric material and cap and the connectivity problem of diffusion impervious layer, the present invention is with organic
Liquid source three-(ethoxymethyl) base silane (MTES) and C2F6For reaction raw materials, PECVD technique is used to prepare low k SiOFCH
Thin film.This low-k materials thin film has good mechanical performance and electric property, can be as the surface of porous ultralow k connected medium
Sealing of hole layer, thus improve the adhesive property between ultralow-k material film thin film and cap, diffusion impervious layer, improve integrated circuit mutual
Reliability even.
List of references
[1] International Technology Roadmap for Semiconductors 2011,
www.itrs.net.
[2] S. J. Ding. Chem. Vap. Deposition 2001, 7, 4.
[3] P. F. Wang. et al. Appl. Phys. A. 2001, 72, 721.
[4] E. P. Guyer. et al. J. Mater. Res. 2006, 21, 882.
[5] M. D. Ong. et al. Mater Res.Soc. Symp. Proc. 2006, 914,15.
[6] A. Grill. et al. Appl. Phys. 2008, 103, 054104/1. 。
Summary of the invention
It is an object of the invention to provide that a kind of k value is low, hardness is strong for porous connected medium surface is carried out sealing of hole
Thin film and preparation method thereof.The thin film of the present invention not only has relatively low k value, also have the highest Young's modulus and hardness and
Good insulating properties.
The preparation method of the thin film for porous connected medium surface-sealing provided by the present invention, it uses PECVD skill
Art, with MTES steam and C2F6Gas is reaction source, has deposited SiOFCH sealing material thin film；Specifically comprise the following steps that
(1) wafer of the porous connected medium that at ambient temperature, will be covered with low-k k is put into plasma and is increased
On pallet in the reaction cavity of extensive chemical vapour deposition (PECVD) equipment, and underlayer temperature is heated to 200～400 DEG C；
(2) by the control of liquid flow gauge (LFM), by three-(ethoxymethyl) base silane (MTES) with firm discharge 1～5
G/min is passed through carburator, and the MTES after vaporization is loaded in reaction cavity by He gas, wherein the flow of carrier gas He be 2000～
5000sccm；
(3) another road reacting gas C2F6Control to be directly entered in reaction cavity by mass flowmenter (MFC), its flow
It is 200～2000 sccm；
(4) C2F6, three-(ethoxymethyl) base silane (MTES) after vaporization mix in reaction cavity with He carrier gas, treat
When pressure in reaction cavity arrives setting value 3～7 torr, stablizing 1～2 min, open radio-frequency power supply, frequency is
13.56MHz, radio-frequency power is 300～700 watts；I.e. obtain the described thin film for porous connected medium surface-sealing.
In the present invention, the thickness of described thin film was controlled by the time of PECVD.
In the present invention, containing Si-F, Si-O, Si-CH in described thin film3Composition, referred to as SiOFCH material film.This is thin
Film has relatively low dielectric constant, and k value is 2.8～3.3；Under the electric field intensity of 1MV/cm, leakage current density is 10-9A/cm2Number
Magnitude, Young's modulus is 16.21～37.33 GPa, and hardness is 1.25～3.03 GPa.
Present invention have the advantage that
(1) thin film that the present invention provides has excellent uniformity, and preparation process is simple, controllability is good, it is adaptable to
Large-scale mass production in industry.
(2) the sealing material thin film that prepared by the present invention has the mechanical property of excellence, and Young's modulus is 16.21～37.33
GPa, hardness is 1.25～3.03 GPa.
(3) sealing material prepared by the present invention not only has significantly lower than SiO2, the k value of the cap material such as SiON,
Also there are the insulating properties of excellence, up to 10 under the external electric field of 1MV/cm-9A/cm2The order of magnitude.
(4) material film provided by the present invention is possible not only between the low k films such as porous connected medium SiCOH effectively
Connect and sealing of hole, simultaneously the most again can and cap, diffusion barrier material between stick effectively.
Accompanying drawing explanation
Fig. 1 is Fourier transform infrared spectroscopy (FTIR) figure of SiOFCH thin film.
Detailed description of the invention
1, the wafer that will be covered with low-k (k) porous connected medium puts into plasma enhanced chemical vapor deposition
(PECVD) on the pallet in the reaction cavity of equipment, this porous material is porous SiCOH ultra-low-k film, or is porous SiO2Thin film.Close
Close cavity, then chamber vacuum degree is evacuated to 0.02～0.03 torr.
2, underlayer temperature is risen to 200～400 DEG C, then pass to He gas, gas piping is preheated, prevented not
The liquid source completely vaporized is condensate in tube wall.
3, by the control of LFM, MTES is passed through carburator with firm discharge for 1g/min, the MTES after vaporization is passed through
He gas is loaded in reaction cavity, and wherein the flow of carrier gas He is 5000sccm.
4, another road reacting gas C2F6Controlling to be directly entered in reaction cavity by mass flowmenter (MFC), its flow is
200-2000 sccm。
5, in reaction cavity, C2F6Mix with MTES and the He carrier gas after vaporization, the pressure in question response cavity
When arriving setting value 3～7 torr, then stablize 1～2 min, be then turned on radio-frequency power supply (frequency is 13.56MHz), radio frequency merit
Rate is 300～700 watts.After deposition 1～4 min, i.e. complete the sealing of hole to super low-k porous connected medium thin film.
In order to measure the electric property of above-mentioned PECVD thin film, with low resistance silicon chip (resistivity is 0.001-0.01 Ω cm)
For substrate, process conditions same as described above are used to prepare this thin film.Utilize electron beam evaporation equipment thick in film surface length
Degree is circle (its a diameter of 400-420 μm) the aluminum electrode of 300nm, simultaneously certain thickness aluminum, shape silicon chip back side is also long
Become metal/PECVD thin film/quasiconductor (MOS) test structure.By the measurement of the capacitance-voltage characteristics of this structure is extracted
Dielectric constant, and obtain reliable average k-value by multimetering.Additionally, by the survey of the I-E characteristic to this structure
Amount obtains leakage current density.The mechanical property of thin film and chemical composition are respectively by nano-hardness tester and Fourier transform infrared light
Spectrum (FTIR) records.
Accompanying drawing 1 is the FTIR figure of this thin film, 810cm-1 And 1080cm-1The neighbouring peak position that absorbs corresponds to the Si-O of thin film
Structure, 935cm-1Neighbouring absworption peak is corresponding to Si-F structure.This shows C2F6F element in gas has been incorporated into silicon oxide film
In, being mixed with of F element helps reduce the k value of thin film.1260cm-1Neighbouring absworption peak derives from Si-CH3Stretching vibration,
Show in this thin film containing a certain amount of CH3Group, its incorporation similarly helps to reduce the k value of thin film.
Subordinate list one lists at different C2F6The performance of the thin film obtained under flow.When MTES flow is fixed as 1g/min,
C2F6When flow changes between 200-2000sccm, the Young's modulus of obtained thin film is 16.21-37.33 GPa, hardness
For 1.25-3.03 GPa, all show the mechanical property of excellence；Under 1MV/cm electric field intensity, leakage current density is in 10- 9A/cm2The order of magnitude, shows extraordinary insulating properties.Work as C2F6Flow is that the k value obtained by 500sccm is minimum, reaches
2.85.Now Young's modulus and the hardness of this thin film is respectively 31.35Gpa and 2.75Gpa, leaks under the electric field intensity of 1MV/cm
Electric current density is 4.3 × 10-9A/cm2, therefore show the mechanical characteristic of excellence and good insulating properties.
Subordinate list
The different C of subordinate list 12F6The SiOFCH film performance prepared under flow
Claims (3)
1. the preparation method for the thin film of porous connected medium surface-sealing, it is characterised in that specifically comprise the following steps that
(1) wafer of the porous connected medium that at ambient temperature, will be covered with low-k k puts into the anti-of PECVD device
Answer on the pallet in cavity, chamber vacuum degree is evacuated to 0.02 ~ 0.03 torr, and underlayer temperature is heated to 200～400
℃；
(2) by the control of liquid flow gauge, three-(ethoxymethyl) base silane is passed through vaporization with firm discharge 1～5 g/min
Device, the MTES after vaporization is loaded in reaction cavity by He gas, and wherein the flow of carrier gas He is 2000～5000sccm；
(3) another road reacting gas C2F6By mass flowmenter control be directly entered in reaction cavity, its flow be 200～
2000 sccm；
(4) C2F6, three-(ethoxymethyl) base silane after vaporization mixes in reaction cavity with He carrier gas, in question response cavity
Pressure when arriving setting value 3～7 torr, stablize 1～2 min, open radio-frequency power supply, frequency is 13.56MHz, radio-frequency power
It it is 300～700 watts；I.e. obtain the described thin film for porous connected medium surface-sealing.
2. the preparation method of the thin film for porous connected medium surface-sealing as claimed in claim 1, it is characterised in that institute
The thickness stating thin film was controlled by the time of PECVD.
3. use the thin film for porous connected medium surface-sealing that the preparation method described in claim 1 obtains.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198015A (en) * | 1997-04-25 | 1998-11-04 | 日本电气株式会社 | Multilevel interconnecting structure in semiconductor device and method of forming the same |
| CN1651159A (en) * | 2004-01-23 | 2005-08-10 | 气体产品与化学公司 | Cleaning CVD chambers following deposition of porogen-containing materials |
| CN1873924A (en) * | 2005-06-01 | 2006-12-06 | 株式会社瑞萨科技 | Semiconductor manufacture method |
| CN103258734A (en) * | 2013-05-16 | 2013-08-21 | 复旦大学 | SiCOH thin film and preparation method thereof |
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2014
- 2014-04-29 CN CN201410175490.9A patent/CN103956331B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198015A (en) * | 1997-04-25 | 1998-11-04 | 日本电气株式会社 | Multilevel interconnecting structure in semiconductor device and method of forming the same |
| CN1651159A (en) * | 2004-01-23 | 2005-08-10 | 气体产品与化学公司 | Cleaning CVD chambers following deposition of porogen-containing materials |
| CN1873924A (en) * | 2005-06-01 | 2006-12-06 | 株式会社瑞萨科技 | Semiconductor manufacture method |
| CN103258734A (en) * | 2013-05-16 | 2013-08-21 | 复旦大学 | SiCOH thin film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| PECVD法沉积氟碳掺杂的氧化硅薄膜表征;丁士进，张庆全，等;《无机材料学报》;20011130;第16卷(第6期);全文 * |
| preparation of ultra low-k porous sioch films from rong-type siloxane with unsaturated hydrocarbon side chains by spin-on desposition;丁士进，张卫，等;《CHIN.PHYS.LETT》;20101230;第27卷(第2期);全文 * |
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