CN101436538A - Method of forming porous film and computer-readable recording medium - Google Patents

Method of forming porous film and computer-readable recording medium Download PDF

Info

Publication number
CN101436538A
CN101436538A CNA2008101303345A CN200810130334A CN101436538A CN 101436538 A CN101436538 A CN 101436538A CN A2008101303345 A CNA2008101303345 A CN A2008101303345A CN 200810130334 A CN200810130334 A CN 200810130334A CN 101436538 A CN101436538 A CN 101436538A
Authority
CN
China
Prior art keywords
film
mentioned
plasma
dielectric film
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2008101303345A
Other languages
Chinese (zh)
Inventor
大岛康弘
井出真司
柏木勇作
宫谷光太郎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokyo Electron Ltd
Original Assignee
Tokyo Electron Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tokyo Electron Ltd filed Critical Tokyo Electron Ltd
Publication of CN101436538A publication Critical patent/CN101436538A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/42—Silicides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02203—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being porous

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Formation Of Insulating Films (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The invention provides a film forming method of multiple aperture plasma membrane and a recording medium readable for computers. Plasma treatment is carried out to the SiOCH film surface formed through a plasma body CVD method using organo-silicone compound raw material to form a surface densification layer; Plasma treatment is carried out further, and then the CHx radix and OH radix is discharged through the surface densification layer from the SiOCH film under the surface densification layer in a controlled rate, thereby steadily forming a porous structure and low dielectric constant film.

Description

The film build method of multiple aperture plasma membrane and computer-readable recording medium
Technical field
The present invention relates to the formation method of common dielectric film, particularly the formation method of SiOCH film.
Background technology
Nearest by the semiconductor device of miniaturization in, for the very large purpose semiconductor element that will form is electrically connected, use so-called multi-layer wiring structure on substrate.In multi-layer wiring structure, the interlayer dielectric lamination that is embedded with Wiring pattern is a plurality of, and the contact hole of the Wiring pattern of one deck by forming in above-mentioned interlayer dielectric interconnects with the Wiring pattern of adjacent layer or with diffusion zone in the substrate.
This by the semiconductor device of miniaturization in, in interlayer dielectric, complicated Wiring pattern near and form, the distribution of the signal of telecommunication that is caused by the parasitic capacitance in the interlayer dielectric postpones (RC delay) becomes serious problem.That is to say,, make the long-pending of wiring resistance R and distribution capacitor C reduce to become important as the distribution technology of high speed, low consumption electrification.
Therefore, particularly in nearest so-called sub-micron (submicron) or be called as in the ultra micro refinement semiconductor device of deep-submicron (sub-quarter micron), as the interlayer dielectric that constitutes multi-layer wiring structure, the use dielectric constant is about 3～3.5 the silicon oxide layer that is added with F (SiOF film), and the replacement dielectric constant is about 4 silicon oxide layer (SiO in the past 2Film).
But in the SiOF film, the reduction of dielectric constant also has the limit, at such SiO 2In the dielectric film of substrate, be difficult to reach require in the semiconductor device of the generation below design rule 0.1 μ m less than 3.0 dielectric constant.
On the other hand, dielectric constant lower, so-called low-k (low-K) dielectric film has various materials, but the interlayer dielectric that uses in multi-layer wiring structure need use dielectric constant not only low but also have high mechanical strength and to the material of heat treated stability.
The SiOCH film has sufficient mechanical and can realize dielectric constant below 2.5, and can utilize the CVD method of the manufacturing process that is suitable for semiconductor device to form, be expected to as the low-k interlayer dielectric film that in follow-on ultrahigh speed semiconductor device, uses.
In the past, reported that the SiOCH film can utilize the parallel plate-type plasma processing apparatus to form.But the SiOCH film that utilizes common CVD technology to form has the dielectric constant between 3～4, about 2.5 the dielectric constant that can't reach that organic SOG, SiLK coating-type dielectric films such as (registered trade marks) reached.
As one of method of the dielectric constant that will in the SiOCH film, realize being equal to, consider film is formed multiple aperture plasma membrane with such coating-type dielectric film.For example record in patent documentation 9: the SiOCH film that will utilize the CVD method to pile up is exposed to microwave plasma excitated hydroperoxyl radical, CHx base, OH base is discharged to outside the film from the SiOCH film of piling up at substrate, thereby obtains the technology of multiple aperture plasma membrane.
But, thereby like this SiOCH film enforcement hydrogen plasma processing that forms being carried out in the method for modification, in handling, modification needs delicate control on substrate, and in the volume production operation, be difficult to stably carry out modification and handle.
Promptly, in above-mentioned prior art, by the hydroperoxyl radical of plasma exciatiaon Si-CHx key in the film or Si-OH key are cut off, cut CHx base and the OH base form with methane (CH4) molecule is released to outside the film, when the modification processing was carried out under only condition, the methane molecule of Xing Chenging played the effect that the SiOCH film is expanded, its result like this, form the space in film, be emptying aperture, the dielectric constant of SiOCH film reduces.
But in this modification was in the past handled, when the modification treatment conditions departed from narrow optimum scope, the SiOCH film did not expand and shrinks on the contrary since with the increase of shrinking density together, the dielectric constant of film can increase on the contrary.
Patent documentation 1:WO2005/045916 communique
Patent documentation 2: the spy opens the 2005-093721 communique
Patent documentation 3: the spy opens the 2004-158793 communique
Patent documentation 4: the spy opens the 2004-158794 communique
Patent documentation 5: the spy opens the 2005-017085 communique
Patent documentation 6: the spy opens the 2005-093721 communique
Patent documentation 8: the spy opens the 2005-175085 communique
Patent documentation 7: the spy opens the 2005-026468 communique
Patent documentation 8:WO2003/019645 communique
Patent documentation 9: special table 2003-503849 communique
Patent documentation 10: special table 2002-538604 communique
Patent documentation 11: the spy opens the 2004-200626 communique
Patent documentation 12: the spy opens flat 8-236520 communique
Patent documentation 13:WO2001/097296 communique
Patent documentation 14: the spy opens the 2004-158793 communique
Patent documentation 15:WO2001/097269 communique
Patent documentation 16: the spy opens the 2004-200626 communique
Patent documentation 17: special table 2003-503849 communique
Patent documentation 18: special table 2002-538604 communique
Patent documentation 19: the spy opens the 2002-110636 communique
Patent documentation 20: the spy opens flat 7-106299 communique
Patent documentation 21: the spy opens flat 6-84888 communique
Patent documentation 22: No. the 2506539th, Japanese patent gazette
Non-patent literature 1:A.Grill and D.A.Neumayer, J.Appl.Phys.vol.94, No.10, Nov.15,2003
Summary of the invention
One aspect of the present invention provides a kind of film build method of multiple aperture plasma membrane, it is characterized in that, comprising: utilize the organo-silicon compound raw material to form the operation of the dielectric film that contains organic functional base and hydroxyl on substrate; Carry out densification that above-mentioned organic functional base is removed in above-mentioned dielectric film surface, form the operation of surface densification layer in above-mentioned dielectric film surface; Be exposed to by the hydroperoxyl radical of plasma exciatiaon with the dielectric film that will be formed with above-mentioned surface densification layer, above-mentioned organic functional base and hydroxyl are removed, in above-mentioned dielectric film body, form the operation of emptying aperture thus.
Another aspect of the present invention provides a kind of computer-readable recording medium, it is characterized in that, the program that the film forming that records and utilize all-purpose computer control basal plate treatment system, makes the aforesaid substrate treatment system to carry out the multiple aperture plasma membrane on the silicon substrate is handled, the aforesaid substrate treatment system is passed through first substrate board treatment and the second substrate board treatment be combined into, and the film forming of above-mentioned multiple aperture plasma membrane is handled and comprised: the operation that processed substrate is imported above-mentioned first substrate board treatment; In above-mentioned first substrate board treatment, utilize the organo-silicon compound raw material on aforesaid substrate, to form the operation of the dielectric film that contains organic functional base and hydroxyl; In above-mentioned first substrate board treatment, carry out densification that above-mentioned organic functional base is removed in above-mentioned dielectric film surface, form the operation of surface densification layer in above-mentioned dielectric film surface; The above-mentioned processed substrate that carries out above-mentioned densification is imported the operation of above-mentioned second substrate board treatment; With in above-mentioned second substrate board treatment, the dielectric film that will be formed with above-mentioned surface densification layer is exposed to by the hydroperoxyl radical of plasma exciatiaon, and above-mentioned organic functional base is removed, and forms the operation of emptying aperture thus in above-mentioned dielectric film body.
According to the present invention, the film forming of multiple aperture plasma membrane is undertaken by following operation: utilize the organo-silicon compound raw material to form the dielectric film that contains organic functional base and hydroxyl on substrate; Carry out densification that above-mentioned organic functional base and hydroxyl are removed in above-mentioned dielectric film surface, form the density surface densification layer higher than the density of above-mentioned dielectric film body in above-mentioned dielectric film surface; The dielectric film that will be formed with above-mentioned surface densification layer is exposed to by the hydroperoxyl radical of plasma exciatiaon, and above-mentioned organic functional base and hydroxyl are removed, and forms emptying aperture thus in above-mentioned dielectric film body.Thus, form in the operation at above-mentioned emptying aperture, the common brief note that contains in the above-mentioned dielectric film is the CH of CHx 3, C 2H 5... be discharged to outside the film with controlled speed in organic functional base and hydroxyl (OH), thus the contraction of the dielectric film can suppress above-mentioned emptying aperture effectively and form the time.Its result, the density increase of dielectric film is suppressed, and can access the multiple aperture plasma membrane of low-k.
In addition, after film formation process, only film forming unstrpped gas is cut off like this, proceed the supply of plasma gas and oxidizing gas and the supply of plasma power, thus, the generation of the particle that film formation process causes when finishing is suppressed effectively, and the rate of finished products of film forming improves widely.
Description of drawings
Fig. 1 is the figure that represents the structure of the one-tenth membrane treatment appts that uses in the present invention.
Fig. 2 (A)～(C) is the figure of the film build method of expression first execution mode of the present invention.
Fig. 3 is the figure that represents to be used in the present invention the structure of the substrate board treatment that multiple aperture plasma membrane forms.
Fig. 4 is another figure that represents to be used in the present invention the structure of the substrate board treatment that multiple aperture plasma membrane forms.
Fig. 5 is the figure that the effect to above-mentioned first execution mode of the present invention describes.
Fig. 6 is the table of the k value of the treatment conditions of operation of presentation graphs 2 (A)～(C) and resulting multiple aperture plasma membrane.
Fig. 7 is the figure of the FTIR spectrum of the SiOCH film that obtains by first execution mode of the present invention of expression.
Fig. 8 is the figure that is illustrated in the structure of the cluster type substrate board treatment that uses in first execution mode of the present invention.
Fig. 9 is the flow chart that the film build method of the first embodiment of the invention that the cluster type substrate board treatment of Fig. 7 carries out is used in expression.
Figure 10 (A)～(D) is the figure of the film build method of expression second execution mode of the present invention.
Figure 11 A is the figure of processing time and leakage current relation in expression second execution mode of the present invention.
Figure 11 B is O in expression second execution mode of the present invention 2The figure of/Ar flow-rate ratio and leakage current relation.
Figure 12 A is the figure of the variation of processing time and leakage current in expression second execution mode of the present invention.
Figure 12 B is O in expression second execution mode of the present invention 2/ H 2The figure of flow-rate ratio and leakage current relation.
Figure 13 is the table of the experiment condition of expression second execution mode.
Figure 14 is another table of the experiment condition of expression second execution mode.
Figure 15 is the figure of the XPS spectrum of the SiOCH film that obtains by above-mentioned second execution mode of the present invention of expression.
Figure 16 is the figure of the SIMS distribution map of the SiOCH film that obtains by above-mentioned second execution mode of the present invention of expression.
Figure 17 is the figure that the part of Figure 16 is amplified expression.
Figure 18 is the figure of expression the 3rd execution mode of the present invention.
Figure 19 is the figure that is illustrated in the structure of the cluster type substrate board treatment that uses in above-mentioned the 3rd execution mode of the present invention.
Figure 20 is the table of the experiment condition of expression the 4th execution mode of the present invention.
Figure 21 (A)～(C) is the figure that the 4th execution mode of the present invention is described.
Figure 22 (A)～(C) is another figure that the 4th execution mode of the present invention is described.
Figure 23 (A), (B) are another figure that the 4th execution mode of the present invention is described.
Embodiment
[first execution mode]
Fig. 1 represents to be used in the present invention the structure of the parallel plate-type substrate board treatment 11 that the film forming of dielectric film handles.
With reference to Fig. 1, substrate board treatment 11 comprises by the container handling 12 that constitutes through the conductive materials such as aluminium of anodized, utilize exhaust apparatus 14 such as turbomolecular pump to carry out exhaust by exhaust outlet 13, in above-mentioned container handling 12 inside, support and be provided with the pedestal 17 that keeps processed substrate W by columned base supports platform 16 roughly.Said base 17 also works as the lower electrode of parallel plate-type substrate board treatment 11, between base supports platform 16 and pedestal 17, is provided with insulators 18 such as pottery.In addition, above-mentioned container handling 12 is grounded.
Be provided with refrigerant circuits 19 in said base brace table 16 inside, circulate in above-mentioned refrigerant circuits 19 by making refrigerant, said base 17 and the processed substrate W on it when processing substrate technology, are controlled as the substrate temperature of expectation.
In addition, the sidewall of above-mentioned container handling 12 is provided with gate valve 15, under above-mentioned gate valve 15 opened state, moves into or take out of processed substrate W with respect to above-mentioned container handling 12.
Above-mentioned exhaust apparatus also is connected with the device 36 of removing the evil, and the above-mentioned device 36 of removing the evil makes the discharge gas harmlessization from container handling 12 of being discharged by exhaust apparatus 14.For example, the above-mentioned device 36 of removing the evil can utilize the catalyst of regulation to make atmosphere gas burning or thermal decomposition, thereby is converted to harmless material.
In said base brace table 16, freely be provided with the lifter pin 20 of the handing-over that is used to carry out the processed substrate W of semiconductor by elevating mechanism (not shown) lifting.In addition, be formed with recessed discoideus part in the upper central portion of said base 17, above-mentioned recessed discoideus part is provided with the electrostatic chuck (not shown) with processed substrate W corresponding shape.Be positioned in the processed substrate W on the said base 17 owing to be applied in direct voltage by above-mentioned electrostatic chuck Electrostatic Absorption.
In addition, above said base 17, with said base 17 almost parallels, be provided with spray head 23 with the relative mode of processed substrate W on the said base 17.
On the face relative of above-mentioned spray head 23 with said base 17, be provided with the battery lead plate 25 that constitutes by aluminium etc. with a plurality of gas supply holes 24, above-mentioned spray head 23 is supported on the top section of above-mentioned container handling 12 by electrode support 26.In the inside of above-mentioned spray head 23, be formed with another refrigerant circuits 27, circulate in above-mentioned refrigerant circuits 27 by making refrigerant, when processing substrate technology, above-mentioned spray head 23 is maintained desired temperatures.
In addition, gas introduction tube 28 is connected with above-mentioned spray head 23, and on the other hand, above-mentioned gas ingress pipe 28 by not shown mass flow controller separately and valve etc., and maintains trimethyl silane ((CH 3) 3SiH) material container 29 of raw material, the oxidant gas source 30 that maintains oxygen, the Ar gas source 31 that maintains argon gas (Ar) connect.
Unstrpped gas and processing gas from above-mentioned gas source 29～31, mix in the hollow bulb that is formed at spray head 23 inside (not shown) by gas introduction tube 28, be supplied to the processing space of the near surface of above-mentioned processed substrate W from the gas supply hole 24 of above-mentioned spray head 23.
In addition, second high frequency electric source 32 is connected with above-mentioned spray head 23 by second adaptation 33, and it is 450kHz～300MHz that above-mentioned high frequency electric source 32 is supplied with frequency to above-mentioned spray head 23, preferably the high frequency power of 13.56～150MHz scope.By supplying with the high frequency power of high like this frequency, above-mentioned spray head 23 works formation plasma above-mentioned container handling 12 in as upper electrode.Plasma source can also be suitable for microwave mode, the ICP mode.
In addition, the substrate board treatment 11 of Fig. 1 has the control part 34 that the action of processing unit 11 integral body that the film forming that is included on the processed substrate W is handled is controlled.Microprocessing unit), the microcomputer control device of memory etc. constitutes above-mentioned control part 34 is by having MPU (Micro Processing Unit:, to be used for according to the rules processing sequence to the procedure stores of installing each one and controlling at memory, according to each one of this presetting apparatus.
The summary of the film build method of Fig. 2 (A)～(C) expression first execution mode of the present invention.
With reference to Fig. 2 (A), silicon substrate 41 is imported in the substrate board treatment 11 of Fig. 1, at 13.3～13333Pa, preferably under the pressure of 100～1000Pa, under the substrate temperature of room temperature～200, with Ar gas with 100～6000SCCM, the flow of 100～1000SCCM preferably, with oxygen with 50～2000SCCM, the flow of 50～200SCCM preferably, with trimethyl silane organic silicon compound gas such as (3MS) with 50～2000SCCM, preferably the flow of 50～200SCCM is supplied in the above-mentioned container handling 12, in addition, by above-mentioned high frequency electric source 32 with 50～3000W, preferably the power of 100～750W is the high frequency of 13～150MHz to above-mentioned spray head 23 supply frequencies, thus, on the surface of above-mentioned silicon substrate 41, with the film forming speed of 500～2000nm/ branch, with 100～1000nm, preferably the formation of the thickness of 200～400nm is the main composition element with Si and oxygen, and contain the so-called SiOCH film 42 of carbon and hydrogen.
For example, the film forming of above-mentioned SiOCH film, under the pressure of 300Pa, under the substrate temperature of 45, with Ar gas with the flow of 600SCCM, with oxygen with the flow of 100SCCM, the flow of trimethyl silane gas with 100SCCM is supplied in the above-mentioned container handling 12, and to supply with frequencies with the power of 500W to above-mentioned spray head 23 be the high frequency of 13.56MHz, can above-mentioned SiOCH film 42 be formed the thickness of about 400nm with the film forming speed that 1500nm/ divides.In aforesaid substrate processing unit 11, above-mentioned spray head 23 is set at 25mm with the interval of pedestal 17.Interval than broad can reduce plasma damage, improves homogeneity.Described interval is preferably in the scope of 10～500mm.
The SiOCH film of Xing Chenging has than higher, about dielectric constant of about 3～4 like this.
Next, in the present embodiment, in the operation of Fig. 2 (B), structure with respect to above-mentioned Fig. 2 (A), in identical parallel plate-type substrate board treatment 11, cut off the supply of above-mentioned trimethyl silane gas, on the other hand, continue the supply of above-mentioned Ar gas and oxygen and high frequency power, from room temperature up under 200 ℃ the substrate temperature, preferably with above-mentioned SiOCH film 42 film forming the time under the identical substrate temperature, plasma treatment is carried out on surface to above-mentioned SiOCH film 42, on its surface, utilizes oxygen to replace the CH on above-mentioned surface 3, C 2H 5In CHx base and OH base, begin with 5～20nm from the surface, preferably the thickness of 10～15nm formation oxygen concentration high and SiO 2The densification layer 43 of approaching composition.The modified process of Fig. 2 (B) also can use surface plasma, magnetic controlled plasma, and perhaps the oxygen radical that is formed by microwave plasma illustrated in fig. 3 carries out.Because the modified process of Fig. 2 (B) is undertaken by the low-power plasma body, can reduce the damage to SiOCH film 42.The ratio of described densification layer is preferably 0.5～20% of described SiOCH film 42 thickness, and particularly 2.5～7.5%.
The operation of above-mentioned Fig. 2 (B) was for example carried out 10～300 seconds, preferably 10～60 seconds.After this, in the present embodiment, further in the operation of Fig. 2 (C), the substrate that will be formed with the densification layer of Fig. 2 (B) imports the microwave plasma processing apparatus shown in Fig. 3,4, utilization is by the hydroperoxyl radical of plasma exciatiaon, SiOCH film under the above-mentioned densification layer 43 is carried out modification, in film, form the hole, form the multiple aperture plasma membrane 42A that SiOCH forms.
With reference to Fig. 3, plasma processing apparatus 50 comprises and is formed with the container handling 51 of handling space 51A, in above-mentioned container handling 51, in the above-mentioned processing space 51A, is provided with the substrate holder 52 that keeps processed substrate W.Above-mentioned container handling 51 at exhaust port 51C, by to surround the space 51B that aforesaid substrate keeps the mode of platform 52 to form, carries out exhaust by APC51D and exhaust apparatus 11E.
Aforesaid substrate keeps platform 52 to be provided with heater 52A, and above-mentioned heater 52A is driven by driver circuit 52B by power supply 52C.
In addition, in above-mentioned container handling 51, be provided with substrate and move into/take out of mouthful 51g and with the gate valve 51G of its interlock, move into/take out of mouthful 51g by aforesaid substrate and move into processed substrate W in the container handling 11 or from wherein taking out of.
On above-mentioned container handling 51, corresponding with above-mentioned processed substrate W and be formed with peristome, the top board 53 that above-mentioned peristome is made of dielectrics such as quartz glasss clogs.In addition, below above-mentioned top board 53, be provided with the gas access and the compression ring (gas ring) 54 of a plurality of gas introduction ports of being communicated with this gas access, be provided with in the mode relative with above-mentioned processed substrate W.
At this, above-mentioned top board 53 works as microwave window, on the top of above-mentioned top board 53, is provided with the flat plane antenna 55 that is made of radial line slot antenna (radial line slot antenna).
In illustrated embodiment, radial line slot antenna is used as above-mentioned microwave antenna 55, therefore, and above-mentioned antenna 55 configuration plane antenna plate 55B and dispose the slow-wave plate 55A that constitutes by dielectrics such as quartz on top board 53 in the mode of overlay planes antenna 55B.Constitute the lid 55D of conductivity in the mode that covers slow-wave plate 55A.In lid 55D, be formed with cooling collar, top board 53, flat plane antenna plate 55B, slow-wave plate 55A are cooled off, prevent that heat is damaged, to generate stable plasma.
Flat plane antenna plate 55B is formed with at a plurality of slits illustrated in fig. 4 (slot) 55a, 55b, in addition, the coaxial waveguide 56 that is made of external conductor 56A and inner conductor 56B is connected with the central portion of antenna 55, and inner conductor 56B connects above-mentioned slow-wave plate 55A, is connected with the central authorities of flat plane antenna 55B and combination.
Above-mentioned coaxial waveguide 56 is connected with the waveguide road 110B of square-section by the 110A of mode conversion portion, and above-mentioned waveguide 110B combines with microwave source 112 by impedance matching box 111.Therefore, the microwave that forms in above-mentioned microwave source 112 is supplied to flat plane antenna 55B by rectangular waveguide 110B and coaxial waveguide 56.
Fig. 4 at length represents the structure of above-mentioned radial line slot antenna 55.Fig. 4 is the front elevation of above-mentioned flat plane antenna plate 55B.
With reference to Fig. 4 as can be seen, on above-mentioned flat plane antenna plate 55B, a plurality of slit 55a are that concentric circles forms and adjacent slit forms with the direction (being T word shape or Eight characters shape) of quadrature.
Therefore, when microwave when coaxial waveguide 56 is supplied to such radial line slot antenna 55B, microwave along footpath direction expansion and propagate, utilizes above-mentioned slow-wave plate 55A to accept the wavelength compression in antenna 55B this moment.Therefore, microwave is from above-mentioned slit 55a, usually with the direction of flat plane antenna plate 55B approximate vertical on, radiate as circularly polarized wave.
In addition, as shown in Figure 3, in above-mentioned microwave plasma processing apparatus 50, rare gas source 101A and sources of hydrogen 101H, source of oxygen 101O such as Ar, MFC103A, 103H, 103O and separately valve 104A, 104H, 104O and shared valve 106 by separately are connected with above-mentioned compression ring 54.As the front has illustrated, in above-mentioned compression ring 54, keep the mode of platform 52 to be formed with a plurality of gas introduction ports to surround aforesaid substrate equably, its result, above-mentioned Ar gas and hydrogen are imported the processing space 51A in the above-mentioned container handling equably.
When action, the processing space 51A in the above-mentioned container handling 51 utilizes the exhaust by above-mentioned exhaust outlet 51C, is set to the pressure of regulation.In addition, except Ar, can also use rare gas such as Kr, Xe, Ne.
In addition, importing frequency by antenna 115 to above-mentioned processing space 51A from above-mentioned microwave source 112 is the microwave of several GHz, for example 2.45GHz, its result, and going out plasma density at the surface excitation of above-mentioned processed substrate W is 10 11～10 13/ cm 3High-density plasma.
The feature of this plasma is the low electron temperature of 0.5～2eV, and its result in above-mentioned plasma processing apparatus 50, does not have the processing of the plasma damage of processed substrate W.In addition, with plasma exciatiaon together and the free radical that forms along the Surface runoff of processed substrate W, promptly got rid of from handling space 51A, the mutual combination again of free radical is suppressed, and can for example carry out very uniform, effective processing substrate below 500 ℃.
Therefore, in the operation of above-mentioned Fig. 2 (C), in above-mentioned processing space 51A, form low electron temperature plasma like this, when further in this low electron temperature plasma, importing hydrogen by above-mentioned compression ring 54, above-mentioned hydrogen is formed hydroperoxyl radical H* by plasma exciatiaon.The hydroperoxyl radical H that forms *Easily diffuse through above-mentioned densification layer 43, arrive the SiOCH film 42 under it, at this displacement CH 3, C 2H 5In CHx base or OH base.CHx base of being replaced or OH base are emitted as gas by above-mentioned densification layer 43.But CHx base, OH base can not freely pass through in above-mentioned densification layer 43 as hydroperoxyl radical, but with than above-mentioned hydroperoxyl radical pass through speed slowly the speed of Duoing is gently emitted, therefore, preferably heat to improve exhaust velocity.
Its result, in the operation of above-mentioned Fig. 2 (C), CHx base, OH base free in above-mentioned SiOCH film 42 are pressed in forming, and these bases gently are released to outside the film by above-mentioned densification layer 43, and the contraction of the films such as increase of substantial density can not take place in film 42.Therefore, in the above-mentioned SiOCH film 42, above-mentioned CHx base or OH base break away from and are replaced into atom site (site) the formation emptying aperture of hydrogen, by the operation of above-mentioned Fig. 2 (C), in the above-mentioned SiOCH film 42, the body part under the above-mentioned densification film 43 becomes multiple aperture plasma membrane 42A.That is, the operation of Fig. 2 (C) becomes the emptying aperture that forms emptying aperture in above-mentioned SiOCH film and forms operation.
In an example, under 400 ℃ substrate temperature, under the pressure of 267Pa, respectively with flow hydrogen supply and the Ar gas of 200SCCM and 1000SCCM, power with 3kW is the microwave of 2.45GHz to 360 seconds frequency of above-mentioned microwave antenna 55 supplies, carries out the operation of Fig. 2 (C) thus.At this, the substrate temperature of the operation of Fig. 2 (C) is set at, and more than high 100 of the substrate temperature in each operation of above-mentioned Fig. 2 (A), (B), but is no more than 400.When the substrate temperature with Fig. 2 (C) is set at 400 when above, particularly when making large-scale semiconductive integrated circuit (IC) apparatus etc., in the ultra micro refinement transistor that has been formed on substrate by previous operation etc., the distribution map that can produce impurity matter-element element is because the heat of processing substrate and problems such as variation.In addition, the operation of above-mentioned Fig. 2 (C) is preferably in 20～1333Pa, particularly carries out under the processing pressure of 20～650Pa scope.At this moment, preferably use 500W～6kW, particularly the plasma power of 500W～3kW scope.Perhaps, be preferably under the high pressure of 133.3～1333Pa and under the low-power plasma concrete conditions in the establishment of a specific crime, carry out.
In Fig. 5, data A～D is corresponding with the experiment of carrying out under condition shown in Figure 6.
With reference to Fig. 5 as can be known, form under the situation of operation at the emptying aperture that the oxidation processes of above-mentioned Fig. 2 (B) is omitted, directly transferred to after the film formation process at the SiOCH film of Fig. 2 (A) Fig. 2 (C), the dielectric constant that obtains is about 2.8 (treatment conditions A), when the hydrogen plasma of Fig. 2 (C) is handled, removing promptly of CHx base or OH base takes place, on the other hand, SiOCH film 42 also shrinks, and does not have to produce that the emptying aperture that can satisfy forms and the reduction of dielectric constant.
Relative therewith, can find out, implementing under 10～60 seconds the situation of oxidation processes operation of Fig. 2 (B), the value of dielectric constant reduces along with oxidation treatment time, for example when the above-mentioned oxidation processes operation of having carried out 60 seconds, be reduced to 2.55 at dielectric constant under the treatment conditions B, be reduced to 2.52, dielectric constant is reduced to 2.4 under treatment conditions D at dielectric constant under the treatment conditions C.This dielectric constant is the value that comprises under the state of above-mentioned densification layer 43, and under the situation of after the operation of above-mentioned Fig. 2 (C) above-mentioned densification layer 43 being removed, the value of dielectric constant can further reduce.
In addition, under the condition identical with the treatment conditions A of above-mentioned Fig. 6, but the pressure when making film forming is in the experiment (treatment conditions E) of 400Pa, confirms: carrying out reaching 2.28 dielectric constant under 10 seconds the situation of oxygen plasma treatment of Fig. 2 (B).Can think, pressure during by such control SiOCH film film forming, the oxygen plasma irradiation time after the film forming and emptying aperture form the hydrogen plasma irradiation time in the operation, the dielectric constant of resulting SiOCH film can be controlled, dielectric constant can be further reduced.
That is, the pressure during owing to SiOCH film 42 film forming is located at more than the 133.3Pa, preferably more than the 300Pa, carries out oxygen plasma treatment and/or hydrogen plasma then and handles, so the k value of described SiOCH film can be reduced to less than 3.0.Further, the pressure when film forming is located at 400Pa when above, and described k value can be reduced to below 2.3.
Fig. 7 represent will be by Fig. 2 (C) densification operation and hydrogen plasma handle the FTIR spectrum of the ultralow dielectric SiOCH film 42A that obtain and compare with the state (As-depo) that only carries out the film forming of Fig. 2 (A).Fig. 7 is the situation that is formed with the state of densification layer 43 on above-mentioned SiOCH film 42A.In addition, among Fig. 7, the evaluation of each absworption peak is carried out according to non-patent literature 1.
With reference to Fig. 7 as can be known, when the film of film that will carry out the processing of densification and hydrogen plasma and As-depo compares, methyl, OH base reduce, on the other hand, with the corresponding position of Si-O-Si cage (cage) structure, absorb increase, this shows because the disengaging of CHx base, OH base has been formed with emptying aperture in fact in SiOCH film 42.In addition, can think that under the state of Fig. 2 (C), the absorption corresponding with the Si-O-Si network increases, so mechanical strength also increases.
Fig. 7 shows, forms operation by the multiple aperture plasma membrane that carries out Fig. 2 (C) after the surface densification operation of Fig. 2 (B), in fact forms emptying aperture in above-mentioned SiOCH film 42A, and film 42A becomes multiple aperture plasma membrane.
Fig. 8 represents to carry out the summary of cluster (cluster) type substrate board treatment 60 of the operation of above-mentioned Fig. 2 (A)～(C).
With reference to Fig. 8, above-mentioned cluster type substrate board treatment 60 comprises: vacuum carrying room 601; Be arranged on the movable carrying arm 602 in the above-mentioned vacuum carrying room 601; Be connected with above-mentioned vacuum carrying room 601, take in the process chamber 200 of previous substrate board treatment 11; Combine with above-mentioned vacuum carrying room 601, take in the process chamber 300 of previous substrate board treatment 50; With the load locking room 603,604 that combines with above-mentioned vacuum carrying room 601.
On above-mentioned process chamber 200,300, above-mentioned vacuum carrying room 601, load locking room 603 and 604, be connected with not shown exhaust unit.
In addition, above-mentioned process chamber 200,300, load locking room 603,604, be connected with above-mentioned vacuum carrying room 601 by opening and closing freely gate valve 601a～601b, 601d and 601e respectively, by in the above-mentioned gate valve any is open, with processed substrate from above-mentioned vacuum carrying room 601 conveyances to any substrate processing chamber, perhaps from any substrate processing chamber conveyance to above-mentioned vacuum carrying room 601.
In addition, on above-mentioned load locking room 603 and 604, be respectively arranged with and open and close gate valve 603a and 604a freely,, take in the wafer case C1 of a plurality of processed substrates to above-mentioned load locking room 603 fillings by above-mentioned gate valve 603a is open.Equally, by above-mentioned gate valve 103b is open, take in the wafer case C2 of a plurality of processed substrates to above-mentioned load locking room 604 fillings.
When carrying out processing substrate, for example, processed substrate W 0By above-mentioned carrying arm 602 from box C1 or C2 by above-mentioned vacuum carrying room 601 conveyances to process chamber 200, processed substrate after in above-mentioned process chamber 200, finishing dealing with, by above-mentioned carrying arm 102 by above-mentioned vacuum carrying room 601 conveyances in above-mentioned process chamber 300.The substrate W that will finish dealing with in above-mentioned process chamber 300 is accommodated among the box C2 of the box C1 of above-mentioned load locking room 603 or load locking room 604.
Fig. 8 has represented to be combined with the example of 2 process chambers on vacuum carrying room 601, but also can be for example on the face 601A of vacuum carrying device or 601B further the connection processing container, use as so-called multi-cavity chamber system.Thus, can carry out film forming, densification and hydrogen plasma efficiently and handle, thereby can form the low-density film with high production rate.
At this moment, because film forming and densification are carried out in same processing unit, and the hydrogen plasma processing is carried out in other processing unit, perhaps film forming processing, densification and hydrogen plasma are handled and are carried out in different processing unit respectively, can improve film forming and handle whole productivity ratio.
Fig. 9 is the flow chart that the action to cluster type substrate board treatment 60 integral body of Fig. 8 describes.
With reference to Fig. 9, in step 1, above-mentioned processed substrate W conveyance in above-mentioned process chamber 200, is carried out the corresponding operation with above-mentioned Fig. 2 (A) in above-mentioned container handling 11, carry out the accumulation of SiOCH film 42.
Then, in step 2, in same container handling 11, keep plasma, and continue the supply of oxygen and Ar gas, only cut off the supply of above-mentioned organosilan unstrpped gas, corresponding with the operation of above-mentioned Fig. 2 (B), form surface densification layer 42A on the surface of above-mentioned SiOCH film 42.
Then, in step 3, with above-mentioned processed substrate W from above-mentioned process chamber 200 conveyances to process chamber 300, the emptying aperture that is carried out Fig. 2 (C) by Fig. 3,4 substrate board treatment 50 forms operation.
The substrate board treatment 60 of Fig. 8 comprises that control device 600A is used for controlling so a series of processing substrate technology.In addition, the formation operation of the surface densification layer 42A of step 2 also can be carried out in process chamber 300, but after the surface densification layer 42A of step 2 forms, handle in order to carry out hydrogen plasma, need heat up, therefore, be preferably in and only carry out hydrogen plasma in other process chamber 300 and handle.
Above-mentioned control device 600A is actually all-purpose computer, reads in the storage medium that records the program coding unit corresponding with the processing of Fig. 7, according to the said procedure coding unit, each one of aforesaid substrate processing unit 60 is controlled.
In addition, in the present embodiment, the film formation process of above-mentioned Fig. 2 (A) is not limited to the plasma CVD operation, also can utilize working procedure of coating to carry out.
[second execution mode]
The summary of the film build method of Figure 10 (A)～(D) expression second execution mode of the present invention.In the drawings, for the part that the front has illustrated, mark identical reference marks, also omission explanation.
With reference to Figure 10 (A)～(E), Figure 10 (A)～(C) is identical with previous Fig. 2 (A)～(C), and present embodiment is characterised in that, in the operation of Figure 10 (D), utilizes by the oxygen radical O of plasma exciatiaon *, or oxygen radical O *With hydroperoxyl radical H *Further the structure that the operation by Figure 10 (C) is obtained is handled.
For example, the structure that operation by Figure 10 (C) is obtained is arranged in the same microwave plasma processing apparatus, under same substrate temperature (for example 400 ℃), processing pressure is set at 20 roughly the same～1333Pa, preferably processing pressure, for example 260Pa of 20～650Pa, supplying with Ar gas, supply with oxygen with the flow of 200SCCM with the flow of 250SCCM, is the microwave of 2.45GHz with the power of 500W～2kW, the power supply frequency of for example 2kW.Thus, above-mentioned SiOCH film 42A, particularly its surface is by oxygen radical O *Modification is changed to SiOCH film 42B.The result that this modification is handled on the surface of above-mentioned SiOCH film 42A, handles the damage that produces by the hydrogen plasma of the oxygen plasma treatment of Figure 10 (B) or Figure 10 (C) and is eliminated or alleviates.
Figure 11 A, 11B and Figure 12 A, 12B represent the variation of the leak current characteristic of the SiOCH film that caused by such modification treatment process.Wherein, Figure 11 A, Figure 11 B are illustrated under various oxygen/Ar throughput ratio, the leakage current of SiOCH film and the relation in processing time.Figure 12 A, Figure 12 B are illustrated under various oxygen/hydrogen flowing quantity ratio, the leakage current and the relation in modification processing time.
In whole experiments of Figure 11 A, 11B and Figure 12 A, 12B, as the SiOCH film, use utilizes the one-tenth membrane treatment appts 11 of above-mentioned Fig. 1, on p type silicon substrate, under the pressure of 100Pa, under 25 ℃ temperature, supply with trimethyl silane, supply with oxygen, supply with Ar gas with the flow of 100SCCM with the flow of 600SCCM with the flow of 100SCCM, be the film that the high frequency of 27.12MHz forms with the power supply frequency of 250W.
The leakage current of SiOCH film preferably is controlled at 1 * 10 -8A/cm 2Below.
The details of the experiment that the modification that following Figure 13 represents only to utilize oxygen radical to carry out Figure 10 (D) is handled.
With reference to Figure 13, in experiment #11, the SiOCH film (hereinafter referred to as initial SiOCH film) that obtains for operation by above-mentioned Figure 10 (C), in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, flow with 500SCCM is supplied with Ar gas, with the flow hydrogen supply of 1000SCCM, be the microwave of 2.45GHz with 120 seconds frequency of the power of 2kW irradiation, carry out hydrogen plasma and handle.
In experiment #12, for above-mentioned initial SiOCH film, in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 500SCCM, with the flow hydrogen supply of 1000SCCM, 120 seconds frequency of power irradiation with 2kW is the microwave of 2.45GHz, carry out hydrogen plasma and handle, then, whole gas and microwave power cut off 55 seconds after, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 2000SCCM, supply with oxygen with the flow of 200SCCM, 5 seconds frequency of power irradiation with 1.5kW is the microwave of 2.45GHz, carries out oxygen plasma treatment.
In experiment #13, for above-mentioned initial SiOCH film, in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 500SCCM, with the flow hydrogen supply of 1000SCCM, 120 seconds frequency of power irradiation with 2kW is the microwave of 2.45GHz, carry out hydrogen plasma and handle, then, whole gas and microwave power cut off 55 seconds after, under the pressure of 400Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 2000SCCM, supply with oxygen with the flow of 200SCCM, 5 seconds frequency of power irradiation with 1.5kW is the microwave of 2.45GHz, carries out oxygen plasma treatment.
In experiment #14, for above-mentioned initial SiOCH film, in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 500SCCM, with the flow hydrogen supply of 1000SCCM, 120 seconds frequency of power irradiation with 2kW is the microwave of 2.45GHz, carry out hydrogen plasma and handle, then, whole gas and microwave power cut off 55 seconds after, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 2000SCCM, supply with oxygen with the flow of 5SCCM, 20 seconds frequency of power irradiation with 1.5kW is the microwave of 2.45GHz, carries out oxygen plasma treatment.
In experiment #15, for above-mentioned initial SiOCH film, in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 500SCCM, with the flow hydrogen supply of 1000SCCM, 120 seconds frequency of power irradiation with 2kW is the microwave of 2.45GHz, carry out hydrogen plasma and handle, then, whole gas and microwave power cut off 55 seconds after, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 2000SCCM, supply with oxygen with the flow of 200SCCM, 20 seconds frequency of power irradiation with 1.5kW is the microwave of 2.45GHz, carries out oxygen plasma treatment.
In experiment #16, for above-mentioned initial SiOCH film, in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 500SCCM, with the flow hydrogen supply of 1000SCCM, 120 seconds frequency of power irradiation with 2kW is the microwave of 2.45GHz, carry out hydrogen plasma and handle, then, whole gas and microwave power cut off 55 seconds after, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 2000SCCM, supply with oxygen with the flow of 5SCCM, 40 seconds frequency of power irradiation with 1.5kW is the microwave of 2.45GHz, carries out oxygen plasma treatment.
In experiment #17, for above-mentioned initial SiOCH film, in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 500SCCM, with the flow hydrogen supply of 1000SCCM, 120 seconds frequency of power irradiation with 2kW is the microwave of 2.45GHz, carry out hydrogen plasma and handle, then, whole gas and microwave power cut off 55 seconds after, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 2000SCCM, supply with oxygen with the flow of 200SCCM, 40 seconds frequency of power irradiation with 1.5kW is the microwave of 2.45GHz, carries out oxygen plasma treatment.
The details of the experiment that the modification that utilizes oxygen radical and hydroperoxyl radical to carry out Figure 10 (D) shown in Figure 14 presentation graphs 12A, the 12B is handled.
In experiment #1, identical with above-mentioned experiment #11, for the initial SiOCH film that in the operation of above-mentioned Figure 10 (C), forms, in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, flow with 500SCCM is supplied with Ar gas, with the flow hydrogen supply of 1000SCCM, be the microwave of 2.45GHz with 120 seconds frequency of the power of 2kW irradiation, carry out hydrogen plasma and handle.
In experiment #2, for above-mentioned initial SiOCH film, in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 500SCCM, with the flow hydrogen supply of 1000SCCM, 100 seconds frequency of power irradiation with 2kW is the microwave of 2.45GHz, carry out hydrogen plasma and handle, then, add inbound traffics 5SCCM oxygen, to make plasma power be 1.5kW, in addition, under identical conditions, carry out 20 seconds hydrogen-oxygen plasma treatment.
In experiment #3, for above-mentioned initial SiOCH film, in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 500SCCM, with the flow hydrogen supply of 1000SCCM, 60 seconds frequency of power irradiation with 2kW is the microwave of 2.45GHz, carry out hydrogen plasma and handle, then, add inbound traffics 5SCCM oxygen, to make plasma power be 1.5kW, in addition, under identical conditions, carry out 60 seconds hydrogen-oxygen plasma treatment.
In experiment #4, for above-mentioned initial SiOCH film, in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 500SCCM, flow hydrogen supply with 1000SCCM, supplying with oxygen with the flow of 5SCCM, is the microwave of 2.45GHz with 120 seconds the frequency of power irradiation of 2kW, carries out the hydrogen-oxygen plasma treatment.
In experiment #5, for above-mentioned initial SiOCH film, in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 500SCCM, with the flow hydrogen supply of 1000SCCM, 100 seconds frequency of power irradiation with 2kW is the microwave of 2.45GHz, carry out hydrogen plasma and handle, then, add inbound traffics 25SCCM oxygen, to make plasma power be 1.5kW, in addition, under identical conditions, carry out 20 seconds hydrogen-oxygen plasma treatment.
In experiment #6, for above-mentioned initial SiOCH film, in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, supply with Ar gas with the flow of 500SCCM, with the flow hydrogen supply of 1000SCCM, 60 seconds frequency of power irradiation with 2kW is the microwave of 2.45GHz, carry out hydrogen plasma and handle, then, add inbound traffics 25SCCM oxygen, to make plasma power be 1.5kW, in addition, under identical conditions, carry out 60 seconds hydrogen-oxygen plasma treatment.
In addition, in not shown experiment #7, for above-mentioned initial SiOCH film, in the substrate board treatment 50 of Fig. 3, under the pressure of 267Pa, under 400 ℃ temperature, flow with 500SCCM is supplied with Ar gas, with the flow hydrogen supply of 1000SCCM, supplies with oxygen with the flow of 25SCCM, 120 seconds frequency of power irradiation with 2kW is the microwave of 2.45GHz, carries out the hydrogen-oxygen plasma treatment.
In addition, in above-mentioned Figure 13, whole experiments of 14, the gap of plasma processing apparatus 50 (gap) length setting is 55mm.
With reference to Figure 11 A and 11B or Figure 12 A and 12B as can be known, by carrying out such utilize reprocessing that hydroperoxyl radical and oxygen radical carry out or the reprocessing that only utilizes oxygen radical to carry out, can make formed SiOCH film keep low dielectric constant, compare with the situation of termination being handled in modification in the stage of Figure 10 (C), can improve its leak current characteristic, can realize 1 * 10 -8A/cm 2Following leakage current density.
More particularly, in experiment #1 that oxygen radical handles is handled, do not carried out to the hydroperoxyl radical that was only carrying out 120 seconds, average dielectric constant was 3.79, leakage current is 1.58 * 10 -8A/cm 2, and after the hydroperoxyl radical that carried out 100 seconds is handled, to carry out with the oxygen flow of 5SCCM among 20 seconds the experiment #2 that utilizes the processing that hydroperoxyl radical and oxygen radical carry out, average dielectric constant is 3.64, leakage current is 1.29 * 10 -8A/cm 2After the hydroperoxyl radical that carried out 60 seconds is handled, to carry out with the oxygen flow of 5SCCM among 60 seconds the experiment #3 that utilizes the processing that hydroperoxyl radical and oxygen radical carry out, average dielectric constant is 3.29, leakage current is 7.82 * 10 -9A/cm 2Carry out 120 seconds the experiment #4 that utilizes the processing that hydroperoxyl radical and oxygen radical carry out with the oxygen flow of 5SCCM from beginning, average dielectric constant is 3.36, leakage current is 3.53 * 10 -9A/cm 2After the hydroperoxyl radical that carried out 100 seconds is handled, to carry out with the oxygen flow of 25SCCM among 20 seconds the experiment #5 that utilizes the processing that hydroperoxyl radical and oxygen radical carry out, average dielectric constant is 3.34, leakage current is 8.55 * 10 -9A/cm 2After the hydroperoxyl radical that carried out 60 seconds is handled, to carry out with the oxygen flow of 25SCCM among 60 seconds the experiment #6 that utilizes the processing that hydroperoxyl radical and oxygen radical carry out, average dielectric constant is 3.24, leakage current is 6.98 * 10 -9A/cm 2
In addition, in experiment #11 that oxygen radical handles is handled, do not carried out to the hydroperoxyl radical that was only carrying out 120 seconds, #1 was identical with experiment, and average dielectric constant is 3.79, leakage current is 1.58 * 10 -8A/cm 2, and after the hydroperoxyl radical that carried out 120 seconds is handled, to carry out with the oxygen flow of 200SCCM among 5 seconds the experiment #12 that utilizes the processing that oxygen radical carries out, average dielectric constant is 3.72, leakage current is 1.47 * 10 -8A/cm 2After the hydroperoxyl radical that carried out 120 seconds is handled, to carry out with the oxygen flow of 200SCCM among 5 seconds the experiment #13 that under the pressure of 400Pa, utilizes the processing that oxygen radical carries out, average dielectric constant is 3.53, leakage current is 8.94 * 10 -9A/cm 2After the hydroperoxyl radical that carried out 120 seconds is handled, to carry out with the oxygen flow of 5SCCM among 20 seconds the experiment #14 that utilizes the processing that oxygen radical carries out, average dielectric constant is 3.50, leakage current is 7.60 * 10 -9A/cm 2After the hydroperoxyl radical that carried out 120 seconds is handled, to carry out with the oxygen flow of 200SCCM among 20 seconds the experiment #15 that utilizes the processing that oxygen radical carries out, average dielectric constant is 3.50, leakage current is 8.54 * 10 -9A/cm 2After the hydroperoxyl radical that carried out 120 seconds is handled, to carry out with the oxygen flow of 5SCCM among 40 seconds the experiment #16 that utilizes the processing that oxygen radical carries out, average dielectric constant is 3.35, leakage current is 4.75 * 10 -9A/cm 2After the hydroperoxyl radical that carried out 120 seconds is handled, to carry out with the oxygen flow of 200SCCM among 40 seconds the experiment #17 that utilizes the processing that oxygen radical carries out, average dielectric constant is 3.58, leakage current is 7.96 * 10 -9A/cm 2
Figure 11 A, 11B be according to above-mentioned Figure 13, and the oxygen when the expression oxygen radical is handled is the processing time of 0.1 and 0.025 sample and the relation of leakage current with respect to the flow-rate ratio of Ar gas.In addition, in Figure 11 A, 11B, represented not carry out the result of the standard specimen (#11) that oxygen radical handles in the lump and the pressure when oxygen radical handled is made as the result of the sample of 400Pa.Among Figure 11 A, transverse axis is represented the processing time, and among Figure 11 B, transverse axis is represented oxygen/Ar throughput ratio.
By Figure 11 A, 11B as can be known, leakage current values sharply reduced along with the oxygen radical processing time, and especially, the flow-rate ratio of the oxygen/Ar gas when oxygen radical is handled is the leakage current of 0.0025 sample, and specific discharge is lower than the leakage current that is 0.1 sample.
By the relation of Figure 11 A, 11B as can be known, such oxygen radical is handled and is preferably carried out carrying out more than 20 seconds even more ideal more than 10 seconds.
Figure 12 A, 12B represent oxygen radical handle in oxygen with respect to the flow-rate ratio of hydrogen be 0.005 and 0.025 sample, based on the processing time of Figure 14 and the relation of leakage current.In addition, Figure 12 B represents not carry out the result of the standard specimen (#1) that oxygen radical handles in the lump.Among Figure 12 A, transverse axis is represented the processing time, and among Figure 12 B, transverse axis is represented oxygen/hydrogen flowing quantity ratio.
With reference to Figure 12 A, 12B as can be known, though leakage current with carrying out of handling of oxygen radical and reduce, oxygen was 0.025 sample with respect to the flow-rate ratio of hydrogen during particularly oxygen radical was handled, when processing time during above 60 seconds, leakage current changes rising into.
On the other hand, oxygen is in 0.005 the experiment, even use the longer processing time, also not find the increase of k value and leakage current with respect to the flow-rate ratio of hydrogen in oxygen radical is handled.
By the relation of Figure 12 A, 12B as can be known, such oxygen radical is handled and is preferably carried out carrying out more than 20 seconds even more ideal more than 10 seconds.
Figure 15 represents the XPS (Xray-photoelectron spectroscopy:X ray photoelectric spectrum) of the SiOCH film sample that will be obtained by the experiment of the #12 of the #2 of above-mentioned Figure 13 and above-mentioned Figure 14 thereby the XPS spectrum of the SiOCH film sample that spectrum and comparative control experiment by the #1 of #1 Figure 14 of above-mentioned Figure 13 obtain compares.
With reference to Figure 15 as can be known, in the sample of comparative control, observe and Si-C or the corresponding peak of Si-Si key, and, utilize H no matter be by carrying out the reprocessing of Figure 10 (D) *(H free radical) and O *Under the situation that (O free radical) carries out, still only utilize O *Under the situation of carrying out, these keys in the film all reduce, disappear in fact.The surface that this means the SiOCH film is by O *Be modified as rich SiO 2Composition.
Si, the O that Figure 16,17 expressions are tried to achieve for the SiOCH film of such formation, the XPS depth profile (depth profile) of C.
With reference to Figure 16,17, the data that are recited as " Ref " are illustrated in the sample that stops in the operation till Figure 10 (A)～(C), are recited as " Post O 2" data be illustrated in the sample that in the operation of Figure 10 (D) SiOCH film surface has been carried out oxygen plasma treatment, be recited as " H 2+ O 2" sample be illustrated in and utilize oxygen radical and nitrogen free radical that the sample of handling has been carried out on SiOCH film surface in the operation of Figure 10 (D).
Especially, according to the enlarged drawing of Figure 17 as can be known, thickness at the SiOCH film that constitutes benchmark sample (#1 and #11) is the surface portion of 20～30nm, be formed with by the affected layer of the hydroperoxyl radical of Figure 10 (C) reduction, in such surface damage layer, the ratio of Si-C key increases, and can produce problems such as leakage current increase, dielectric constant increase.In addition we know, handle by hydrogen plasma, in the surface densification layer 43 of the oxygen enrichment that forms on the surface of above-mentioned SiOCH film 42A, the disengaging that produces oxygen.That is, can think that the surface densification layer that forms has the thickness about 20～30nm in the operation of above-mentioned Figure 10 (B).
Relative therewith, in the present embodiment, in the operation of Figure 10 (D), carry out processing of oxygen plasma treatment or hydrogen plasma and oxygen plasma treatment as reprocessing, the exhaustion of the oxygen of such SiOCH film surface portion is replenished, and then affected layer is repaired the reduction of the dielectric constant shown in realization Figure 11 A, the figure B and the reduction of leakage current.
In addition, the operation of above-mentioned Figure 10 (D) under the situation of using the cluster type substrate board treatment 60 that has before illustrated in Fig. 8, can be undertaken by proceed above-mentioned processing in above-mentioned process chamber 300.
[the 3rd execution mode]
In the execution mode that has formerly illustrated, residual on formed porous Si OCH film 42A have a densification layer 43, and such densification layer 43 has the effect that the dielectric constant that makes SiOCH film integral body increases, and therefore wishes to be removed.
Therefore, in the present embodiment, further, utilize for example Ar sputter process or CMP operation, above-mentioned densification layer 43 is removed removing in the operation with the densification layer of back to back Figure 18 of operation of above-mentioned Fig. 2 (C).
For example, in the operation of Figure 18, use plasma processing apparatus 400, flow with 5SCCM under 280 ℃ substrate temperature is supplied with Ar gas, such as supplying with frequency with the power of 300W to high frequency coil is the high frequency of 13.56MHz, power with 300W applies the high frequency bias that frequency is 2MHz to processed substrate, carries out 130 seconds sputter etching, above-mentioned densification layer 43 can be removed thus.As a result, the surface densification layer is removed, and about 2.2 dielectric constant can be reduced to 2.0, thereby can form the ultralow dielectric film.
Figure 19 represents to comprise the structure of cluster type substrate board treatment 60A of film formation process of present embodiment of the operation of above-mentioned Figure 18.But in Figure 19, the corresponding part of part with before having illustrated marks identical reference marks, omits its explanation.
With reference to Figure 19, substrate board treatment 60A comprises the process chamber 400 that combines with above-mentioned vacuum carrying room 601 by gate valve 601c, in the example shown in the figure, is provided with the ICP plasma processing apparatus in above-mentioned process chamber 400.In addition, also microwave plasma processing apparatus can be arranged in the process chamber 400.
Therefore, in above-mentioned process chamber 300, processed substrate after the operation of the operation of Fig. 2 (C) or Figure 10 (D) finishes passes through vacuum processing chamber 601 conveyances to above-mentioned process chamber 400 by above-mentioned transport mechanism 602, and the surface densification layer that utilizes sputtering method to carry out Figure 18 is removed processing.
In addition, also can with in above-mentioned process chamber 300, the operation of the operation of Fig. 2 (C) or Figure 10 (D) the processed substrate after finishing, from above-mentioned load locking room 603 or 604, take out, in another CMP device, carry out the operation of above-mentioned Figure 18.
[the 4th execution mode]
In the operation of Fig. 2 that has formerly illustrated (B) or Figure 10 (B), after the operation by Fig. 2 (A) or Figure 10 (A) forms SiOCH film 42, continue to supply with Ar gas and oxygen and high frequency power, only cut off organosilan unstrpped gas, the surface densification layer of expecting forms operation.
The present inventor finds, during the experiment of above-mentioned Fig. 2 (A)～(C), particularly in the end process of the SiOCH film film formation process of Fig. 2 (A), processed substrate surface produces a large amount of particles sometimes.
Figure 20 represents the experiment that the present inventor carries out.
With reference to Figure 20, in step 1, carry out the film forming of SiOCH film 42, in step 2～4, carry out film forming and finish operation.In addition, the film forming of SiOCH film 42 is carried out under 45 ℃ substrate temperature.
In experiment #21, when cutting off high frequency power, cut off the supply of trimethyl silane unstrpped gas and the supply of oxygen, in step 2, circulate Ar gas after 0.1 second, end process in step 3.In this experiment #21, utilize SEM to observe, confirm at processed substrate surface with 1 * 10 8Individual/cm 2Density be formed with the above particle of particle diameter 0.1 μ m.
In experiment #22, in step 1, continue supply, the supply of oxygen and the supply of Ar gas of trimethyl silane unstrpped gas, cut off high frequency power, in step 2, after 10 seconds, cut off the supply of trimethyl silane unstrpped gas, oxygen and Ar gas.In this experiment #22, utilize SEM to observe, confirm at processed substrate surface with 5 * 10 7Individual/cm 2Density be formed with the above particle of particle diameter 0.13 μ m.
In experiment #23, in step 2, continue the supply of oxygen and Ar gas, and continue the supply of high frequency power, only cut off the supply of trimethyl silane unstrpped gas, in step 3, after 0.1 second, continue the supply of Ar gas, cut off the supply of oxygen and high frequency power.In addition, in step 4, after 10 seconds, cut off the supply of Ar gas.In this experiment #23, utilize particle collector to measure, confirm at processed substrate surface with 0.06/cm 2Density be formed with the above particle of particle diameter 0.13 μ m.
In experiment #24, in step 2, continue the supply of Ar gas and high frequency power, cut off the supply of oxygen and trimethyl silane unstrpped gas, in step 3, after 0.1 second, continue the supply of Ar gas, cut off the supply of high frequency power.And then, in step 4, after 10 seconds, cut off the supply of Ar gas.In this experiment #24, utilize SEM to observe, confirm at processed substrate surface with 2 * 10 7Individual/cm 2Density be formed with the above particle of particle diameter 0.1 μ m.
In experiment #25, in step 2, continue the supply of Ar gas, cut off the supply of trimethyl silane unstrpped gas, oxygen and high frequency power, in step 3, after 10 seconds, cut off the supply of Ar gas.In this experiment #22, confirm at processed substrate surface with 2 * 10 7Individual/cm 2Density be formed with the above particle of particle diameter 0.13 μ m.
In experiment #26, in step 2, continue the supply of trimethyl silane gas, Ar gas and high frequency power, only cut off the supply of oxygen, in step 3, after 0.1 second, continue the supply of Ar gas, cut off the supply of trimethyl silane gas and high frequency power.And then, in step 4, after 10 seconds, cut off the supply of Ar gas.In this experiment #26, utilize SEM to observe, confirm at processed substrate surface with 5 * 10 7Individual/cm 2Density be formed with the above particle of particle diameter 0.13 μ m.
By The above results as can be known, as in experiment #23, in the parallel plate-type substrate board treatment, utilize plasma CVD method to form under the situation of SiOCH film, stop the supply of trimethyl silane unstrpped gas earlier, stop the supply of oxygen and high frequency power afterwards, can suppress particle effectively and produce.
Such film forming end order, in fact be equal with the densification operation of after the film formation process of Fig. 2 (A), carrying out Fig. 2 (B), in the operation of the operation of Fig. 2 formerly (A)～(C) or Figure 10 (A)～(D), from the result, the generation that finishes particle together with the film forming of SiOCH film is minimized.
In addition, the present inventor explores the optimal post-treatment condition that the parallel plate-type substrate board treatment 11 that uses Fig. 1 can suppress the particle generation.
Figure 21 (A)～(C) is illustrated in the processing of above-mentioned Fig. 2 (A), (B), under the processing pressure of the 600Pa that is easy to most to produce particle, changes the situation that the particle under the situation of oxygen plasma treatment time of Fig. 2 (B) produces.In Figure 21 (A)～(C), the gap of substrate board treatment 11 is set at 25mm and substrate temperature is set at 45 ℃, in the operation of Fig. 2 (A), the flow of trimethyl silane gas, oxygen and Ar gas is set at 100SCCM, 100SCCM and 600SCCM respectively, and supply with the high frequency of 6.8 seconds 13.56MHz, carry out the film forming of SiOCH film thus, on the other hand, in the operation of Fig. 2 (B), under the same conditions, only cut off trimethyl silane gas, carry out 20～45 seconds oxygen plasma treatment.In Figure 21 (A)～(C), top figure represents to distribute in the face of particle of substrate surface, and following figure represents the particle grain size distribution that produced.
Figure 21 (A) expression is 20 seconds a situation with the oxygen plasma treatment time set of Fig. 2 (B), can find out most above particles of the about 0.4 μ m of particle diameters that produce.
Relative therewith, Figure 21 (B) expression is 30 seconds a situation with the oxygen plasma treatment time set of Fig. 2 (B), can find out that the generation of the particle that the about 0.4 μ m of particle diameter is above is inhibited, and the particle of generation nearly all is the following particle of particle diameter 0.2 μ m.Being among Figure 21 (C) of 45 seconds with above-mentioned oxygen plasma treatment time set, also observe same trend.
So as can be known according to the result of Figure 21 (A)～(C), same with the result of previous Figure 20, by the oxygen plasma treatment operation of previous Fig. 2 (B) that illustrate was carried out more than 30 seconds, the generation of the particle in the time of can suppressing the film forming end effectively, but when observing the particle below the particle diameter 0.13 μ m, can not suppress the generation of particle effectively, in this particle size range, granule number increases on the contrary.
Relative therewith, and then the operation of above-mentioned Fig. 2 (A), in the operation of Fig. 2 (B), substrate temperature, processing pressure, plasma power keep the same terms, and the particle that the flow that makes trimethyl silane gas, oxygen and Ar gas increases when being 2 times produces situation, shown in Figure 22 (A).
With reference to Figure 22 (A) as can be known, compare with the situation of Figure 21 (C), situation is improved a little, but the following particle of particle diameter 0.1 μ m produces in a large number.
In addition, after Figure 22 (B) is illustrated in and carries out the SiOCH film film formation process of above-mentioned Fig. 2 (A) under the condition identical with the Figure 21 (A) that has before illustrated, under identical treatment conditions, it is 2 times that but the flow that makes oxygen and Ar gas increases, and the particle when carrying out 30 seconds the oxygen plasma treatment operation of Fig. 2 (B) produces situation.
With reference to Figure 22 (B) as can be known, the Ar gas during by the oxygen plasma treatment after such increase film forming and the flow of oxygen can make the generation of particle reduce significantly.
In addition, after Figure 22 (C) is illustrated in and carries out the SiOCH film film formation process of above-mentioned Fig. 2 (A) under the condition identical with the Figure 21 (A) that has before illustrated, under identical treatment conditions, but make processing pressure be reduced to 250Pa, the particle when carrying out 30 seconds the oxygen plasma treatment operation of Fig. 2 (B) produces situation.
With reference to Figure 22 (C) as can be known, in this case, the generation of the particle after film forming is handled also reduces significantly.
Under the low 250Pa of processing pressure when Figure 23 (A) is illustrated in and handles than the film forming of Fig. 2 (A), the situation of the particle generation when when the flow of oxygen and Ar gas being increased handle for the film forming of Fig. 2 (A) 2 times carry out the oxygen plasma treatment of Fig. 2 (B).
With reference to Figure 23 (A) as can be known, any with respect to Figure 22 (B) and (C), particle produces and further is suppressed.
In addition, Figure 23 (B) expression processing pressure during with the film forming of Fig. 2 (A) is set at 500Pa, and the situation of particle generation when carrying out with Figure 23 (A) same film forming end process corresponding with the operation of Fig. 2 (B).
With reference to Figure 23 (B) as can be known, the generation of particle further is suppressed.
By the Fig. 2 (B) that carries out under than the low pressure of the film forming treatment process of Fig. 2 (A) or Figure 10 (A) and under the condition that the flow of oxygen and Ar gas is increased so before having illustrated or the oxygen plasma treatment operation of Figure 10 (B), can further suppress the generation of particle effectively.
In addition, oxygen plasma treatment when such film forming finishes, not only effective under the situation of the film forming of in parallel plate-type substrate board treatment shown in Figure 1, carrying out the SiOCH film, and when in the microwave plasma processing apparatus shown in Fig. 3,4, supply with for example trimethyl silane gas, Ar gas and oxygen and carry out under the situation of film forming of SiCO film also effective.
Above be trimethyl silane (TMS:SiH (CH to the organo-silicon compound raw material 3) 3) situation illustrate that still, organo-silicon compound raw material of the present invention is not limited to trimethyl silane, also can use dimethylsilane (SiH 2(CH 3) 2), tetramethylsilane (Si (CH 3) 4), dimethyldimethoxysil,ne (DMDMOS:Si (CH 3) 2(OCH 3) 2), dimethyldiethoxysilane (Si (CH 3) 2(OC 2H 5) 2), dimethylethoxysilane (Si (CH 3) 2(OC 2H5)), trimethyl methoxyl group silicon (Si (CH 3) 3(OC 2H 5)), methyl triethoxysilane (Si (CH 3) (OC 2H 5) 3), Diethylmethylsilane (Si (C 2H 5) 2(CH 3)), trimethyl ethylsilane (Si (C 2H 5) 2(CH 3) 3), ethoxytrimethylsilane (Si (CH 3) 3(OC 2H 5)), methyldiethoxysilane (DEMS:SiH (OC 2H 5) 2(CH 3)), ethyl trimethoxy silane (Si (C 2H 5) 2(OCH 3) 3) etc.
More than, preferred embodiments of the present invention have been disclosed for illustrative, but the present invention is not limited to this certain embodiments, in the purport that claims are put down in writing, can carry out various distortion changes.
The application of this world advocates to quote the full content of this Japan's patent application in this application based on the patent application 2007-183568 of Japan number priority of application on July 12nd, 2007.
Utilizability on the industry
According to the present invention, the film forming of multiple aperture plasma membrane is undertaken by following operation: utilize organic silication The compound raw material forms the dielectric film that contains organic functional base and hydroxyl at substrate; At above-mentioned electricity Densification that above-mentioned organic functional base and hydroxyl are removed is carried out on the deielectric-coating surface, above-mentioned Dielectric film surface forms the high surface densification of density of the above-mentioned dielectric film body of density ratio Layer; The dielectric film that will be formed with above-mentioned surface densification layer is exposed to by plasma exciatiaon Hydroperoxyl radical is removed above-mentioned organic functional base and hydroxyl, thus at above-mentioned dielectric film body The middle emptying aperture that forms. Thus, form in the operation at above-mentioned emptying aperture, contain in the above-mentioned dielectric film Usually brief note is the CH of CHx3、C 2H 5... Deng organic functional base and hydroxyl (OH) with quilt The speed of control is discharged to outside the film, thus the electricity in the time of can effectively suppressing above-mentioned emptying aperture formation The contraction of deielectric-coating. Its result, the density of dielectric film increases suppressed, can access low Jie The multiple aperture plasma membrane of electric constant.
In addition, after film formation process, only film forming unstrpped gas is cut off like this, proceeded The supply of plasma gas and oxidizing gas and the supply of plasma power thus, become The generation of the particle that membrane process causes when finishing is effectively suppressed, and the yield rate of film forming widely Improve.

Claims (21)

1. the film build method of a multiple aperture plasma membrane is characterized in that, comprises;
Utilize the organo-silicon compound raw material on substrate, to form the operation of the dielectric film that contains organic functional base and hydroxyl;
Carry out densification that described organic functional base is removed in described dielectric film surface, form the operation of surface densification layer in described dielectric film surface; With
The dielectric film that will be formed with described surface densification layer is exposed to by the hydroperoxyl radical of plasma exciatiaon, and described organic functional base and hydroxyl are removed, and forms the operation of emptying aperture thus in described dielectric film body.
2. film build method according to claim 1 is characterized in that:
The operation of described formation dielectric film is being carried out under first temperature of 200 ℃ scope from room temperature by plasma CVD method,
The operation of described formation surface densification layer is being undertaken by plasma treatment under second temperature of 200 ℃ scope from room temperature,
The operation of described formation emptying aperture is carried out under than the 3rd high temperature of described first and second temperature.
3. film build method according to claim 2 is characterized in that:
Described first and second temperature are about 45 ℃, and described the 3rd temperature is about 400 ℃.
4. film build method according to claim 2 is characterized in that:
The operation of described formation dielectric film and described operation of carrying out densification are carried out in same substrate board treatment continuously, and the operation of described formation emptying aperture is carried out in other substrate board treatment.
5. film build method according to claim 4 is characterized in that:
The unstrpped gas of described organo-silicon compound raw material is supplied to described substrate surface with oxidizing gas and inactive gas, carries out described dielectric film thus and form operation; Form operation and then with described dielectric film, keep plasma and continue and supply with described oxidizing gas and inactive gas, only cut off the supply of described unstrpped gas, carry out the operation of described formation surface densification layer thus.
6. film build method according to claim 5 is characterized in that:
By continuing the described inactive gas of supply and cutting off the supply of described plasma and described oxidizing gas, the operation of described formation surface densification layer is finished.
7. film build method according to claim 5 is characterized in that:
The operation of described formation surface densification layer is undertaken by the flow increase that the described dielectric film of the flow-rate ratio that makes described oxidizing gas and inactive gas forms in the operation.
8. film build method according to claim 5 is characterized in that:
The operation of described formation surface densification layer is carried out under than the low processing pressure of described dielectric film formation operation.
9. film build method according to claim 1 is characterized in that:
Described dielectric film is the SiOCH film, described densification operation is by utilizing the operation dielectric film surface that forms on described substrate is handled by the oxygen radical of plasma exciatiaon to constitute, with described surface densification layer form with the concentration than described this height of dielectric film contain aerobic, to contain carbon than the low concentration of described dielectric film body.
10. film build method according to claim 1 is characterized in that:
Described densification operation forms the thickness that is no more than 30nm with described surface densification layer.
11. film build method according to claim 1 is characterized in that:
Carry out described densification operation, make in described dielectric film body, to form the Si-O-Si basket structure.
12. film build method according to claim 2 is characterized in that:
Described dielectric film formation operation and described densification operation are in the parallel plate-type plasma CVD equipment, under the pressure of 100～1000Pa, supply with the plasma power of 100～750W and carry out, described emptying aperture forms operation in microwave plasma processing apparatus, under the pressure of 100～1000Pa, supply with the plasma power of 100～750W and carry out.
13. film build method according to claim 1 is characterized in that:
After described emptying aperture forms operation, also comprise the operation of utilizing oxidizing atmosphere the dielectric film with described surface densification layer to be carried out reprocessing.
14. film build method according to claim 13 is characterized in that:
Described postprocessing working procedures is by being undertaken by the oxygen radical of plasma exciatiaon.
15. film build method according to claim 14 is characterized in that:
In described postprocessing working procedures, also add by the hydroperoxyl radical of plasma exciatiaon.
16. film build method according to claim 13 is characterized in that:
It is continuous that described postprocessing working procedures and described emptying aperture form operation, carries out in same plasma processing apparatus.
17. film build method according to claim 1 is characterized in that:
Also be included in described emptying aperture and form after the operation, the operation that described surface densification layer is removed.
18. film build method according to claim 17 is characterized in that:
The operation of removing of described surface densification layer is carried out after described postprocessing working procedures.
19. film build method according to claim 17 is characterized in that:
Describedly remove the plasma that the operation utilization contains rare gas and carry out sputter.
20. film build method according to claim 18 is characterized in that:
The described operation of removing is undertaken by the cmp operation.
21. a computer-readable recording medium is characterized in that:
The program that the film forming that records and utilize all-purpose computer control basal plate treatment system, makes described base plate processing system to carry out the multiple aperture plasma membrane on the silicon substrate is handled, described base plate processing system passes through first substrate board treatment and the second substrate board treatment be combined into, and the film forming of described multiple aperture plasma membrane is handled and comprised:
Processed substrate is imported the operation of described first substrate board treatment;
In described first substrate board treatment, utilize the organo-silicon compound raw material on described substrate, to form the operation of the dielectric film that contains organic functional base and hydroxyl;
In described first substrate board treatment, carry out densification that described organic functional base is removed in described dielectric film surface, form the operation of surface densification layer in described dielectric film surface;
The described processed substrate that carries out described densification is imported the operation of described second substrate board treatment; With
In described second substrate board treatment, the dielectric film that will be formed with described surface densification layer is exposed to by the hydroperoxyl radical of plasma exciatiaon, and described organic functional base is removed, and forms the operation of emptying aperture thus in described dielectric film body.
CNA2008101303345A 2007-07-12 2008-07-11 Method of forming porous film and computer-readable recording medium Pending CN101436538A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007183568 2007-07-12
JP2007183568A JP2009021442A (en) 2007-07-12 2007-07-12 Method of forming film for porous membrane and computer-readable recording medium

Publications (1)

Publication Number Publication Date
CN101436538A true CN101436538A (en) 2009-05-20

Family

ID=40360817

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2008101303345A Pending CN101436538A (en) 2007-07-12 2008-07-11 Method of forming porous film and computer-readable recording medium

Country Status (3)

Country Link
JP (1) JP2009021442A (en)
KR (1) KR20090006769A (en)
CN (1) CN101436538A (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5164078B2 (en) * 2009-10-05 2013-03-13 国立大学法人東北大学 Low dielectric constant insulating film
JP5164079B2 (en) * 2009-10-21 2013-03-13 国立大学法人東北大学 Method for forming low dielectric constant insulating film
WO2011043337A1 (en) * 2009-10-05 2011-04-14 国立大学法人東北大学 Low dielectric constant insulating film and formation method therefor
KR20150129810A (en) * 2013-03-13 2015-11-20 어플라이드 머티어리얼스, 인코포레이티드 Post treatment for dielectric constant reduction with pore generation on low k dielectric films

Also Published As

Publication number Publication date
KR20090006769A (en) 2009-01-15
JP2009021442A (en) 2009-01-29

Similar Documents

Publication Publication Date Title
CN101310370A (en) Method of forming porous film and computer-readable recording medium
CN100573830C (en) Plasma processing apparatus and method of plasma processing
TWI374472B (en) An improved method for fabricating an ultralow dielectric comstant material as an intralevel or interlevel dielectric in a semiconductor device and electronic device made
US7422776B2 (en) Low temperature process to produce low-K dielectrics with low stress by plasma-enhanced chemical vapor deposition (PECVD)
US7888273B1 (en) Density gradient-free gap fill
US7611996B2 (en) Multi-stage curing of low K nano-porous films
CN100514575C (en) Method for forming dielectric film and device of forming film
US8557712B1 (en) PECVD flowable dielectric gap fill
JP4272424B2 (en) Ultralow dielectric constant material as an in-level or inter-level dielectric of a semiconductor element, method for manufacturing the same, and electronic device including the same
CN100594259C (en) Interface engineering to improve adhesion between low k stacks
US20080105978A1 (en) Method for forming an ultra low dielectric film by forming an organosilicon matrix and large porogens as a template for increased porosity
TW201411721A (en) Improved densification for flowable films
US20020197849A1 (en) Very low dielectric constant plasma-enhanced CVD films
JP2013102174A (en) Method to obtain low k dielectric barrier with superior etching resistivity
TW201142945A (en) Ultra low dielectric materials using hybrid precursors containing silicon with organic functional groups by plasma-enhanced chemical vapor deposition
KR20090060768A (en) Method of forming sioc film using precursor for manufacturing sioc film
TWI490363B (en) Insulator film material, film formation method and insulator film that use the same
US7001854B1 (en) Hydrogen-based phosphosilicate glass process for gap fill of high aspect ratio structures
WO2005098961A1 (en) Method of forming gate insulating film, storage medium and computer program
TW201442148A (en) Controlled air gap formation
JP2003530481A (en) Systems and methods for depositing inorganic / organic dielectric films
CN101436538A (en) Method of forming porous film and computer-readable recording medium
US20040266216A1 (en) Method for improving uniformity in deposited low k dielectric material
KR20050091780A (en) Method and apparatus to improve cracking thresholds and mechanical properties of low-k dielectric material
US7067440B1 (en) Gap fill for high aspect ratio structures

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20090520