CN1384535A - Method of reducing dielectric constant of dielectric film and method of making porous film with low dielectric constant - Google Patents
Method of reducing dielectric constant of dielectric film and method of making porous film with low dielectric constant Download PDFInfo
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- CN1384535A CN1384535A CN 01115624 CN01115624A CN1384535A CN 1384535 A CN1384535 A CN 1384535A CN 01115624 CN01115624 CN 01115624 CN 01115624 A CN01115624 A CN 01115624A CN 1384535 A CN1384535 A CN 1384535A
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Abstract
In the present invention, gas is compressed into dense fluid or supercritical fluid infiltrating to below film in non-solvent high-pressure condition and the pressure is released fast to form pores on the surface of the film. In different pressure releasing rate, the high-pressure film treating process can produce different pore diameter distribution. The greater pressure releasing rate, the greater large diameter pore ratio. Controlling the pressure release properly, optimal pore size, 5-20 nm, may be obtained.
Description
The present invention relates to a kind of method that reduces the dielectric film dielectric constant on the semiconductor chip; Particularly relate to a kind of by the method that reduces the thin-film dielectric constant at the surface of this dielectric film formation hole.
Heal to become under complexity and multi-metal lead preparation technology's the demand at the ULSI assembly, be most commonly used to the dielectric material SiO between isolated plain conductor
2(the about 4.1-4.5 of dielectric constant) do not met use; Chief reason is that with the reduction of line-spacing between the inner conductor, the electric capacity between two leads will increase thereupon.Illustrate with capacitance equation:
C=ke
oA/d k: material dielectric constant e
o: permittivity of vacuum
A: area d: two distance between conductors are under identical dielectric constant condition, and the distance of two leads (d) heals little electric capacity then more greatly; Influence will increase RC (RC delay time time of delay in one's power; R wherein: plain conductor resistance, C: metal interlevel electric capacity) cause the decay of assembly transmission rate.Therefore with the reduction of chip circuit size, coming the control capacitance value with low-k (k＜4.1) material is the most direct method.Dielectric materials is being played the part of the electrical obstruct between conductor, the role who reduces talk (crosstalk) effect and reduce the coupling capacitance amount in chip circuit; Except that dwindling RC time of delay, promoting the transmission rate, sizable benefiting arranged for improving coupled noise.Some organic materials or inorganic material all can reduce dielectric constant at present; Certainly, desirable lowest dielectric constant is 1.0 of an air.Therefore, in present research, the improvement of material dielectric constant is also carried out towards 1.0 directions.According to the chemical attribute of material, we can be divided into it inorganic dielectric materials and organic dielectric materials two big classes.Inorganic material is grown up with chemical vapour deposition technique (CVD) haply, for example the silicon dioxide of doped with fluorine, carbon or hydrogen.Because such manufacturing process equipment and present production equipment are similar, therefore with the fastest developing speed, but the change in dielectric constant of Inorganic Dielectric Material is limited, and its value between 2.5 to 3.7, often has the degree that significantly descends because of the difference of bond atom unlike the organic material dielectric constant approximately.Organic material mainly with rotary coating (Spin On Glass, SOG) mode is carried out the film forming program, dielectric constant often with the difference of material approximately between 2-3.7.As for the material of low-k (k＜2) more, then be to utilize blend in the volatilization of film forming solvent or the dissolving film and the pore structure that forms is reached.Target according to ideal capacitance value 1.0 is pursued, and the dielectric materials of pore type has the development potentiality of desirable.
USP5,470,802, USP5,494,858, USP5,103,288, USP5,548,159, USP5,561,318, USP5,569,058, USP5,661,344, USP5, patents such as 747,880, USP5,750,415, USP5,804,508 have similar porous material production process; That is the difference volatilization degree of contained solvent is made the film hole in the control film.With USP5,494,858 is example, and at first, according to 1: 3: 1: 0.0007 not ear ratio was with TEOS (tetraethylorthosilicate), C
2H
5OH, H
2O and HCl mixed under 60 ℃ 1.5 hours.Gained solution adds the NH of 0.05M
4Behind the OH, must utilize immediately the rotary coating machine with solution coat on chip; NH
4The affiliation that adds of OH speeds the gel speed (gelation rate) of solution, generally adds NH
4The ratio of OH is 1/10 of a liquor capacity.The chip that scribbles gel film places the atmosphere 24 hours that contains saturated alcohol gas under 37 ℃, make film cohesion slaking (aging); Treat that slaking finishes, utilize pressure to change the solvent in the film is expelled, to form voided films.Operating pressure can make solvent be become gaseous state and be stayed hole by liquid state less than an atmospheric pressure; Also can be under near solvent supercriticality or high pressure at super critical condition, make solvent become Compressed Gas and remove.The control of all being careful of these steps is to avoid film dimensions generation excess shrinkage phenomenon (shrinkage effect).Will be with reaction condition, solvent species and variant by the pore volume ratio of said method gained film, diameter, distribution; Comprehensive, pore volume accounts for 20%-95%, the best＞75%; Average diameter is approximately less than 80nm, and optimization person is between 2nm-25nm; When hole account for volume 80% the time, material dielectric constant is approximately less than 1.5.Because the shared volume ratio of film inner pore is bigger, just poorer for surface adhering and heat-resisting handling properties, therefore in order to meet the requirement of some post processors of chip, the levels of general voided films can utilize CVD to plate one deck adhesion coating, as SiO
2Except the adhesion of enhancing effect is arranged, also there is the migration that stops interior material suction of hole or atom to ooze out.
Make the voided films except the above-mentioned solvent evaporates of utilizing, the method that removes blend in the film and make hole is still arranged.With USP5,744,399 is example; Utilize SiO
2Sneak into fullerenes in the process of film forming, utilize dissolution with solvents fullerenes then, or utilize O
2/ or O
3The electricity slurry is oxidized to CO with fullerenes
2And the formation hole.(Fullerenes?can?contain?anywherefrom?32?to?as?many?as?960?carbon?atoms?and?are?all?believed?tohave?the?structure?of?geodesic?domes.)
USP5,785, but 787 utilize UV to decompose or the material (as: Anthroquinone, low melting point Waxes etc.) of low-temperature heat distillation is used as polytetrafluoroethylene (polytetrafluoroethylene, PTFE) blend of film.Prepared 70% hole PTFE film makes dielectric constant originally be reduced to 1.2 from 1.9.Certainly, in application facet, need have the up and down adhesion coating and the base material of this class loose structure are made excellent contact otherwise are very easily peeled off.
Be applicable to the making of the low dielectric voided films of semiconductor fabrication process, do not break away from two above-mentioned class methods: blend removes in solvent evaporates or the film.For the former caused voided films dimensional contraction, with the problem of base material adhesion weak effect; Reach problems such as the interior residual blend of the caused film of the latter easily oozes out in post processor, also one after the other be suggested.Be conceived to the solution of these problems, the present invention will propose to form in the non-solvent mode method of low dielectric voided films at this.
Purpose of the present invention: the purpose of this invention is to provide the method that a cover non-solvent formula is made low dielectric voided films, and the method that reduces the dielectric film dielectric constant.In the method, with the problem on the problem of in the past the caused organic solvent residual of low dielectric voided films production process, blend migration surface, problem that the voided films adherence is low, and the problem of dimensional contraction that the solvent evaporates process produces and propose solution.
The object of the present invention is achieved like this:
A kind of method of making low dielectric voided films provided by the invention comprises the following step:
A) on the semiconductor base material, form a dielectric film;
B) semiconductor substrate that this is formed with dielectric film is put into the atmosphere of a high-pressure inert gas; And
C) pressure of this atmosphere of rapid release, and form hole in the surface of this dielectric film.
Preferably, the inventive method further comprise repeatedly carry out steps A) to step C) obtained until the thickness of a required dielectric film.
Preferably, the step B of the inventive method) this semiconductor substrate that is formed with dielectric film is placed in the high-pressure trough in, and imports this high-pressure inert gas to this high-pressure trough.
Preferably, the inert gas in the inventive method be one not with the gas of film reaction.
Preferably, the inert gas in the inventive method is carbon dioxide, nitrogen, helium, argon gas, ethane, propane, ethene, propylene or its their mist.
Preferably, the dielectric film in the inventive method is the low dielectric inorganic material film that utilizes CVD to deposit, or utilizes the formed low dielectric organic polymer film of rotary coating.Preferably, this low dielectric inorganic material film is SiOF, α-CF or SiOC.Preferably, this low dielectric organic polymer film is polyimide (polyimides) or polytetrafluoroethylene (PTFE).
Preferably, in the inventive method this high-pressure inert gas atmosphere have one near or surpass the pressure of the critical pressure of this inert gas.
Preferably, in the inventive method this high-pressure inert gas atmosphere have one near or surpass the temperature of the critical temperature of this inert gas.
Preferably, this high-pressure inert gas atmosphere is a supercritical fluid in the inventive method.
Preferably, the step C of the inventive method) to reduce the pressure of this atmosphere between the rate of pressure reduction between the 5psi/sec to 110psi/sec.
Preferably, the hole the step C of the inventive method) mainly comprises the hole of diameter range between 5nm ~ 80nm.
Fig. 1 a is the flow chart that non-solvent formula provided by the present invention is made the key step A to C of the method for hanging down the dielectric voided films.Fig. 1 b shows the generalized section of semiconductor base material when each step of Fig. 1 a flow process.In steps A, a dielectric film is formed on the semiconductor base material, for example forms a low dielectric organic polymer film or utilizes CVD to deposit a low dielectric inorganic material film by rotary coating.In step B, this semiconductor substrate that is formed with dielectric film put into a high-pressure trough and import the supercritical fluid of a high-pressure inert gas or this inert gas, wherein high-pressure inert gas or its supercritical fluid will infiltrate the surface of this dielectric film.After a period of time, utilize rapid pressure to discharge means and form hole in the surface of this dielectric film to high-pressure trough.Based on the penetrating power of high-pressure inert gas or its supercritical fluid, each hole forms on the surface of this dielectric film continuously and densely, and can not destroy the adhesion between this dielectric film and base material.If will increase the hole ratio of the unit volume of this dielectric film, can repeatedly carry out steps A ' to the thickness of step C until required dielectric film.
The selection that is applicable to the inert gas among the present invention is a principle to select not the gas with this dielectric film reaction for use, for example: carbon dioxide (CO
2: T
c=31.1 ℃, P
c=1070psi), nitrogen (N
2: T
c=-147 ℃, P
c=491.7psi), helium (He: T=-269.9 ℃, P
c=16.53psi), argon gas (Ar: T
c=-122.4 ℃, P
c=706.3psi) etc.; As for other class gas such as ethane (C
2H
6: T
c=-32.2 ℃, P
c=708.3psi), propane (C
3H
8: T
c=96.7 ℃, P
c=615.8psi), ethene (C
2H
4: T
c=9.9 ℃, P
c=742.1psi), propylene (C
3H
6: T
c=91.9 ℃, P
c=667.2psi) or the mixing of above-mentioned gas also can use.
In the present invention, selecting for use of film can be the low dielectric inorganic material film that utilizes CVD to deposit, as: SiOF, α-CF, SiOC etc.; Can also be to utilize the formed low dielectric organic polymer film of rotary coating, as: polyimide (polyimides), PTFE etc.For the superior surface pore manufacturing capacity of explanation the present invention, will select for use by SiH
4+ N
2O+CF
4Utilize Si-O-C-F low dielectric film that CVD deposits as embodiment Deng gas.
High-pressure inert gas among the present invention is after diffusing into film surface lower floor, through pressure release fast, (suitable step-down pressure range: 5psi/sec ~ 110psi/sec), high-pressure inert gas can reduce because of rapid pressure, causes the gas expansion and causes hole in this dielectric film surface; This kind utilizes gas entropy (entropy, Δ S) to change and the energy that generates forms the method for hole the following points benefit is arranged.At first, utilize the dense gas under the condition of high voltage or make the hole dielectric film between the supercritical fluid of gas, liquid two-phase and there is no the solvent contamination problem; Simultaneously, compared to the low dielectric voided films facture of solvent-gel (sol-gel) formula, the present invention has simplified film gelation, slaking, and operating condition and complicated process such as solvent evaporates.Relatively, because low dielectric voided films of the present invention only forms hole continuously and densely on film surface, so can not destroy the tackability of script film bottom and base material.A hole ratio of wanting in addition can be according to the pore diameter film with corresponding film thickness of growing up earlier, repeat again HIGH PRESSURE TREATMENT, fast release of pressure, and the fabrication steps of long film get final product until required film thickness, as figure one description.Certainly can not take place as the problem that blend in the film in dimensional contraction that solvent evaporates causes and the last handling process oozes out the surface as for other yet.
High voltage thin film handling procedure of the present invention can produce different pore diameters and distribute under different pressure rates of release, the per second pressure rate of release big person of healing, and it is big that the ratio of larger-diameter hole will become; Through controlled pressure rate of release suitably, can get preferable pore size, diameter is approximately between the 5nm-20nm scope.
High pressure non-solvent formula hole facture provided by the present invention is applicable to the holeization of at present all kinds of low-k (k＜4.1) material films.Si-O-C-F film with 2000 dusts is an example, is 5nm-80nm through its diameter range of the formed hole of argon gas super critical condition, and wherein main pore diameter scope is 5nm-50nm, and the preferably is 5nm-20nm.The k value of former film is 2.5-2.8, and after the high pressure holeization, the k value reduces, approximately between 2.2-2.6; If increase the hole ratio of film volume, the k value can reduce again.
The present invention is described in detail below in conjunction with drawings and Examples:
Embodiment under the present invention can use is further understood, and it but not is used to limit the scope of the invention as illustrative purposes only.
Fig. 1 a is the process chart that non-solvent formula provided by the present invention is made the key step A to C of the method for hanging down the dielectric voided films.
Stripping face schematic diagram when Fig. 1 b shows each step in each flow process of Fig. 1 a of semiconductor base material.
Fig. 2 one is applicable to the schematic diagram of serial connection processing (the Multi-chamber cluster tool) system 10 of cabin more than that implements the inventive method, wherein comprise a pressure accumulation groove 18 that stores high-pressure inert gas, a high-pressure trough 12 that is communicated with this pressure accumulation groove 18, and be connected in this high-pressure trough 12 and can carry out CVD or etched reaction cabin 14.One mechanical arm 16 is made the transmission that is used for simplifying semiconductor chip by collocation.Drawing is described as follows: the many cabins of 1.. base material 2.. dielectric film material 10.. serial connection system of processing 18.. pressure accumulation groove 12.. high-pressure trough 12 14.. carry out CVD or etched reaction cabin 16.. mechanical arm
[embodiment 1]
Activate compressor, the supercharging in advance of ultra-high purity argon gas is stored in the pressure accumulation groove, pressure accumulation groove pressure is set 2500psi for.
Will with the chip that the CVD mode is coated with the Si-O-C-F dielectric film of 2000 dusts put into volume be one liter, can be withstand voltage to 10, in the stainless steel pressure groove of 000psi; Be heated to 40 ℃, and moment the argon gas of pressure accumulation groove is imported in the reactive tank, controlled pressure is to 1000psi.After treating 15 minutes, with the pressure in the speed release reaction groove of per second 60psi, the pore diameter scope that is caused is 5nm-70nm, and wherein main pore diameter scope is 5nm-40nm.[embodiment 2]
The reaction program of carrying out is as described in the embodiment 1, wherein reaction pressure 1000psi temperature is 40 ℃, and 30 minutes reaction time is with the pressure in the speed release reaction groove of per second 60psi, the pore diameter scope is 5nm-80nm, and wherein main pore diameter scope is 5nm-60nm.[embodiment 3]
The reaction program of carrying out is as described in the embodiment 1, wherein reaction pressure 1600psi temperature is 40 ℃, and 30 minutes reaction time is with the pressure in the speed release reaction groove of per second 15psi, the pore diameter scope is 5nm-70nm, and wherein main pore diameter scope is 5nm-50nm.[embodiment 4]
The reaction program of carrying out is as described in the embodiment 1, wherein reaction pressure 1600psi temperature is 40 ℃, and 30 minutes reaction time is with the pressure in the speed release reaction groove of per second 30psi, the pore diameter scope is 5nm-80nm, and wherein main pore diameter scope is 5nm-60nm.[embodiment 5]
The reaction program of carrying out is as described in the embodiment 1, wherein reaction pressure 1600psi temperature is 40 ℃, and 30 minutes reaction time is with the pressure in the speed release reaction groove of per second 60psi, the pore diameter scope is 5nm-90nm, and wherein main pore diameter scope is 10nm-60nm.[embodiment 6]
The reaction program of carrying out is as described in the embodiment 1, wherein reaction pressure 1300psi temperature is 40 ℃, and 30 minutes reaction time is with the pressure in the speed release reaction groove of per second 30psi, the pore diameter scope is 5nm-80nm, and wherein main pore diameter scope is 5nm-50nm.[embodiment 7]
The reaction program of carrying out is as described in the embodiment 1, wherein reaction pressure 1300psi temperature is 40 ℃, and 15 minutes reaction time is with the pressure in the speed release reaction groove of per second 30psi, the pore diameter scope is 5nm-80nm, and wherein main pore diameter scope is 5nm-40nm.[embodiment 8]
The reaction program of carrying out is as described in the embodiment 1, wherein reaction pressure 1300psi temperature is 40 ℃, and 15 minutes reaction time is with the pressure in the speed release reaction groove of per second 60psi, the pore diameter scope is 5nm-80nm, and wherein main pore diameter scope is 5nm-50nm.
Claims (14)
1. make the method for hanging down the dielectric voided films for one kind, comprise the following step:
A) on the semiconductor base material, form a dielectric film;
B) semiconductor substrate that this is formed with dielectric film is put into the atmosphere of a high-pressure inert gas; And
C) pressure of this atmosphere of rapid release, and form hole in the surface of this dielectric film.
2. the method for the low dielectric voided films of making as claimed in claim 1 is characterized in that: further comprise and repeatedly carry out steps A) to step C) obtained until the thickness of a required dielectric film.
3. the method for the low dielectric voided films of making as claimed in claim 1 is characterized in that: in step B) in this semiconductor substrate that is formed with dielectric film is put into a high-pressure trough, and import this high-pressure inert gas to this high-pressure trough.
4. the method for the low dielectric voided films of making as claimed in claim 1 is characterized in that: described inert gas be one not with the gas of film reaction.
5. the method for the low dielectric voided films of making as claimed in claim 1, it is characterized in that: described inert gas is carbon dioxide, nitrogen, helium, argon gas, ethane, propane, ethene, propylene or their mist.
6. the method for the low dielectric voided films of making as claimed in claim 1, it is characterized in that: described dielectric film is the low dielectric inorganic material film that utilizes CVD to deposit, or utilizes the formed low dielectric organic polymer film of rotary coating.
7. the method for the low dielectric voided films of making as claimed in claim 6, it is characterized in that: described low dielectric inorganic material film is SiOF, α-CF or SiOC.
8. the method for the low dielectric voided films of making as claimed in claim 6, it is characterized in that: described low dielectric organic polymer film is polyimide or polytetrafluoroethylene.
9. the method for the low dielectric voided films of making as claimed in claim 1 is characterized in that: described high-pressure inert gas atmosphere have one near or surpass the pressure of the critical pressure of this inert gas.
10. the method for the low dielectric voided films of the described making of claim 9 is characterized in that: described high-pressure inert gas atmosphere have one near or surpass the temperature of the critical temperature of this inert gas.
11. the method for the low dielectric voided films of making as claimed in claim 1, it is characterized in that: described this high-pressure inert gas atmosphere is a supercritical fluid.
12. the method for the low dielectric voided films of making as claimed in claim 1 is characterized in that: in step C) to reduce the pressure of this atmosphere between the rate of pressure reduction between the 5psi/sec to 110psi/sec.
13. the method for the low dielectric voided films of making as claimed in claim 1, it is characterized in that: described hole mainly comprises the hole of diameter range between 5nm-80nm.
14. the method for the low dielectric voided films of making as claimed in claim 13, it is characterized in that: described hole mainly comprises the hole of diameter range between 5nm-50nm.
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|---|---|---|---|
| CN 01115624 CN1384535A (en) | 2001-04-28 | 2001-04-28 | Method of reducing dielectric constant of dielectric film and method of making porous film with low dielectric constant |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100353491C (en) * | 2004-01-14 | 2007-12-05 | 三星电子株式会社 | Method of fabricating microelectronic device using super critical fluid |
| CN114506135A (en) * | 2020-11-16 | 2022-05-17 | 河南爱彼爱和新材料有限公司 | Low-dielectric-loss and low-dielectric-loss copper-clad plate, preparation method thereof and prepreg for copper-clad plate |
-
2001
- 2001-04-28 CN CN 01115624 patent/CN1384535A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100353491C (en) * | 2004-01-14 | 2007-12-05 | 三星电子株式会社 | Method of fabricating microelectronic device using super critical fluid |
| US7351635B2 (en) | 2004-01-14 | 2008-04-01 | Samsung Electronics Co., Ltd. | Method of fabricating microelectronic device using super critical fluid |
| CN114506135A (en) * | 2020-11-16 | 2022-05-17 | 河南爱彼爱和新材料有限公司 | Low-dielectric-loss and low-dielectric-loss copper-clad plate, preparation method thereof and prepreg for copper-clad plate |
| CN114506135B (en) * | 2020-11-16 | 2024-03-29 | 河南爱彼爱和新材料有限公司 | Low-dielectric and low-dielectric-loss copper-clad plate, preparation method thereof and prepreg for copper-clad plate |
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