CN100433294C - Method for manufacturing semiconductor device and film-forming system - Google Patents
Method for manufacturing semiconductor device and film-forming system Download PDFInfo
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- CN100433294C CN100433294C CNB2005800023604A CN200580002360A CN100433294C CN 100433294 C CN100433294 C CN 100433294C CN B2005800023604 A CNB2005800023604 A CN B2005800023604A CN 200580002360 A CN200580002360 A CN 200580002360A CN 100433294 C CN100433294 C CN 100433294C
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Abstract
An insulating film (91) composed of CF is formed on a substrate. A protective film including an SiCN film (93) is formed on the insulating film (91). A thin film (94) for hard mask which is composed of SiCO is formed on the protective film using a plasma containing active species of silicon, carbon and oxygen. During the formation of the protective film, an SiC film (92) is formed on the insulating film (91) using a plasma containing active species of silicon and carbon, and then an SiCN film (93) is formed on the SiC film (92) using a plasma containing active species of silicon, carbon and nitrogen.
Description
Technical field
The present invention relates to have manufacture method by the semiconductor device of the dielectric film that carbon constituted of fluoridize, and the film-forming system of making this semiconductor device.
Background technology
As realizing one of method that semiconductor device is highly integrated, the technology that makes circuit become multiple stratification is arranged.In order to form the multiple stratification line construction, and utilize conductive layer to connect n line layer and (n+1) line layer, simultaneously, the zone beyond conductive layer forms the film that is called as interlayer dielectric.SiO
2Film is the typical example of this interlayer dielectric.In the prior art, for the further high speed of the action that makes device, and needs reduce the ratio dielectric constant of interlayer dielectric.According to this requirement, enter people's sight as the carbon film (fluorocarbon film) of the fluoridize of the compound of carbon (C) and fluorine (F).SiO
2The ratio dielectric constant of film is about 4, and for the carbon film of fluoridize, because if the kind of selected unstrpped gas, then than dielectric constant for example below 2.5, therefore, be extremely effective film as interlayer dielectric.
Disclosing in Japanese kokai publication hei 10-144667 communique has a kind of use electron cyclotron resonace (ECR) plasma processing apparatus, goes up the technology of the carbon film that forms fluoridize at semiconductor wafer (hereinafter referred to as wafer).Specifically, utilize the interaction in microwave and magnetic field and cause ECR, make the plasma generation gaseous plasmaization of Ar gas etc., utilize this plasma, make unstrpped gas become plasma, to form the carbon film of fluoridize.
Yet, described in this communique because the carbon film of fluoridize is the film of organic system, so, the gas of this film of etching simultaneously also can etching as the resist film of organic system material.Therefore, carry out under the etched situation, must make the thickness of resist film thicker than the carbon film of fluoridize when former state on the carbon film at fluoridize forms etch-resisting film.In addition, when utilizing the oxygen plasma ashing to remove resist film, can produce the problems such as carbon film of ashing to fluoridize.
Because like this, when the carbon film of etching fluoridize, must on the carbon film of fluoridize, form the film that hard mask is used.The material of the film of using as this hard mask is known silica, silicon nitride etc.But, since these materials than dielectric constant height, therefore, cause interlayer dielectric integral body than dielectric constant height, so improper.
Therefore, present inventor's carborundum (SiCN) film of being conceived to carborundum (SiCO) film of the oxygenation lower than dielectric constant and adding nitrogen is used as the material that hard mask is used.The SiCO film is the silicon carbide film that contains the oxygen of 20 atom % degree, and the SiCN film is the silicon carbide film that contains the nitrogen of 10 atom % degree.Particularly, as the former SiCO film, for example in the time will imbedding in the interlayer dielectric, good with the compactness of silicon nitride film that becomes the barrier layer that prevents copper diffusion usefulness or silicon carbide film as the copper of circuit.In addition, after imbedding copper, when removing the copper on the interlayer dielectric when the grinding copper that is called CMP, having the advantage with respect to the bigger grade of patience of CMP, is very effective film.
Yet, when forming the SiCO film on the carbon film at fluoridize, for example make steam (gas) and the oxygen of organic compound such as trimethyl silane become plasma, at this moment, the carbon of the spike of oxygen and the carbon film of fluoridize reacts, and becomes CO
2And emit.Particularly, for example when heating the carbon film of fluoridize under the atmosphere that only has 1ppm at oxygen, the degassing scale of construction from film is many.Therefore, the surperficial dense property reduction of the carbon film of fluoridize, the result causes the problem with the compactness difference of SiCO film.
In addition,,, can not say with the compactness of the carbon film of fluoridize just finely, worry that also its rate of finished products is low though there is not poor degree to the SiCO film for the SiCN film.Infer that it the reasons are as follows.That is, when forming the SiNC film, make the steam and the nitrogen gas plasmaization of organic compounds such as trimethyl silane, the nitrogen in the plasma soaked into to the carbon film of fluoridize at the film forming initial stage.Soak into the nitrogen to the carbon film of this fluoridize, in film forming, emit, make the dense property reduction of the carbon film of fluoridize.Its result infers that the compactness of the carbon film that SiNC film and fluoridize might be bad.
Summary of the invention
The present invention proposes in view of the above problems, and its purpose is to provide a kind of manufacture method that obtains having the semiconductor device of higher compactness between the film that the hard mask of the carbon film of fluoridize and formation is thereon used.In addition, another object of the present invention is to provide a kind of film-forming system of making this semiconductor device.
According to a first aspect of the invention, provide a kind of manufacture method of semiconductor device, it is characterized in that, comprising: on substrate, form operation by the dielectric film that carbon constituted of fluoridize; On described dielectric film, form the operation of the protective layer that contains the silicon carbide film formation that adds nitrogen; And the plasma that utilizes the spike contain silicon, carbon and oxygen, on described protective layer, form the operation that carborundum by oxygenation constitutes the film that hard mask uses.
The above-mentioned plasma that contains the spike of silicon, carbon and oxygen is the plasma that the activation of the gas of the organic compounds of for example silicon and oxygen is obtained.
The operation that is preferably formed above-mentioned protective layer comprises: utilize the plasma of the spike that contains silicon and carbon, form the auxiliary process of silicon carbide film on described dielectric film; And the plasma that utilizes the spike that contains silicon, carbon and nitrogen, formation adds the auxiliary process of the silicon carbide film of nitrogen on described silicon carbide film.
The operation that is preferably formed above-mentioned protective layer comprises: utilize the plasma that the organic compound gas activation of silicon is obtained, form the auxiliary process of silicon carbide film on described dielectric film; And the plasma that utilizes the spike of the spike of the organic compound contain silicon and nitrogen, on described silicon carbide film, form the auxiliary process of the silicon carbide film that adds nitrogen.
Method of the present invention more specifically also comprises: on the film that described hard mask is used, form the operation of the resist film with certain figure; By described resist film, utilize the described film of plasma etching, obtain having operation with the hard mask of the figure graph of a correspondence of described resist film; With by described hard mask, utilize the operation of the described dielectric film of plasma etching.
From this viewpoint of sending out same, a kind of manufacture method of semiconductor device also is provided, it is characterized in that, comprising: the operation that on substrate, forms the dielectric film that the carbon by fluoridize constitutes; Utilization contains the plasma of the spike of silicon and carbon, forms the operation of silicon carbide film on described dielectric film; And the plasma that utilizes the spike that contains silicon, carbon and nitrogen, the operation of the film that the hard mask that formation is made of the carborundum that adds nitrogen on described silicon carbide film is used.
The described plasma that contains the spike of silicon and carbon obtains plasma for the organic compound gas activation with silicon.In addition, contain the plasma that the described plasma of the spike of silicon, carbon and nitrogen obtains for gas and nitrogen activation with the organic compound of silicon.
According to another viewpoint of the present invention, a kind of film-forming system is provided, it is characterized in that, comprising: first container handling of accommodating substrate; In this first container handling, produce first device of first plasma of the spike that contains carbon and fluorine; Accommodate second container handling of described substrate; In this second container handling, be formed for film forming add nitrogen silicon carbide film atmosphere second the device; Accommodate the 3rd container handling of described substrate; In the 3rd container handling, generate the 3rd device of second plasma of the spike that contains silicon, carbon and oxygen; And the control part of controlling described first, second and the 3rd device, wherein, described each device of described control part control carries out following operation:
(a) in described first container handling, utilize described first device to generate described first plasma, on described substrate, form the operation of the dielectric film that the carbon by fluoridize constitutes;
(b) in described second container handling, utilize described second device to form described atmosphere, on described dielectric film, form the operation of the protective layer that contains the silicon carbide film formation that adds nitrogen; And
(c) in described the 3rd container handling, utilize described the 3rd device to produce described second plasma, on described protective layer, form the operation of the film that hard mask that the carborundum by oxygenation constitutes uses.
Above-mentioned first, second with the 3rd container handling at least two be identical container handling.
From the same viewpoint of the present invention, a kind of film-forming system is provided, it is characterized in that, comprising: first container handling of accommodating substrate; In this first container handling, produce first device of first plasma of the spike that contains carbon and fluorine; Accommodate second container handling of described substrate; Handle gas and carry out flow control and be supplied to first gas supply system in this second container handling containing first of silicon and carbon; Handle gas and carry out flow control and be supplied to second gas supply system in described second container handling containing second of nitrogen; Handle second device of gaseous plasmaization with being supplied to described first and second in described second container handling; With the control part of described first and second devices of control and described first and second gas supply systems, wherein, described each device of described control part control carries out following operation:
(a) in described first container handling, utilize described first device to generate described first plasma, on described substrate, form the operation of the dielectric film that the carbon by fluoridize constitutes;
(b) in described second container handling, utilize described second device to become plasma by the described first processing gas that described first gas supply system is supplied with, on described dielectric film, form the operation of silicon carbide film;
(c) in described second container handling, utilize described second device, to handle gaseous plasmaizations by described first and second of described first and second gas supply systems supply, the operation of the film that the hard mask that formation is made of the carborundum that adds nitrogen on described silicon carbide film is used.
Above-mentioned first container handling is identical container handling with above-mentioned second container handling.
In these film-forming systems, in the device of giving birth to plasma, comprise and for example be used in container handling, taking place the gas of plasma or the feed system of activation energy etc.
Description of drawings
Fig. 1 is the sectional view of an execution mode of expression plasma processing apparatus of the present invention.
Fig. 2 is the upward view of gas supply member of the plasma processing apparatus of Fig. 1.
Fig. 3 is the stereogram of antenna that utilizes the plasma processing apparatus of a cross section presentation graphs 1.
Fig. 4 is the sectional view of manufacturing of representing the semiconductor device of first embodiment of the invention by the process sequence of (a)～(f).
Fig. 5 is the sectional view of manufacturing of representing the semiconductor device of first embodiment of the invention by the process sequence of (g)～(i).
Fig. 6 is the sectional view of manufacturing of representing the semiconductor device of first embodiment of the invention by the process sequence of (j)～(k).
Fig. 7 is the partial cross section figure of the semiconductor device of expression the 3rd execution mode of the present invention.
Fig. 8 is the manufacturing sectional view by the semiconductor device shown in the sequence list diagrammatic sketch 7 of (a)～(f) operation.
Fig. 9 is the result's of an expression reference experiment of the present invention figure.
Embodiment
As Fig. 4～shown in Figure 6; in first execution mode of the present invention, on substrate, form interlayer dielectric 91 that the carbon by fluoridize constitutes successively, as SiCN (the adding fire sand) film 93 of protective layer and as SiCO (the adding siloxicon) film 94 of the first hard mask.Then, on SiCO film 94, become the SiO of the second hard mask
2(silica) film 95.Then, utilize this first and second hard mask 94,95, carry out the etching of fluoridize carbon film 91.Then, in the recess that forms by etching, imbed copper wire.
With reference to Fig. 1～Fig. 3, the plasma processing apparatus as the film-forming system that uses is in this embodiment described.
In Fig. 1, what symbol 1 was represented is container handling for example made of aluminum.In this container handling 1, be provided with the semiconductor wafer (hereinafter referred to as wafer) that is used to place as substrate mounting table 2 W, that for example make by aluminium nitride or aluminium oxide etc.The surface of this mounting table 2 is provided with electrostatic chuck 21, and the electrode of this electrostatic chuck 21 is connected with DC power supply 23 by switch 22.In addition,, also be provided with stream 24, from flowing into coolant that road 25 flows into by in the stream 24 and discharge from flowing out road 26 as thermostatic adjustment medium in the inside of mounting table 2.Utilization is by the coolant in this stream 24 and scheme unshowned heater, and the wafer W on the mounting table 2 is maintained set point of temperature.In addition, mounting table 2 is connected with high frequency electric source 27 with the bias voltage of for example 13.56MHz.
In addition, above mounting table 2, be provided with make by electric conductor (for example aluminium), roughly be discoideus gas supply member (spray head) 3.This gas supply member 3 will be separated into the processing space S 2 of the plasma span S1 and the downside of upside in the container handling 1.Below the gas supply member 3 relative, be formed with a plurality of gas supply holes 31 with mounting table 2.Be formed with in the inside of this gas supply member 3 be communicated with gas supply hole 31 be cancellate gas flow path 32 (with reference to Fig. 2).
The base end side that this gas is supplied with road 33 branches into branched pipe 33a and 33b.TMS (trimethyl silane: SiH (CH as the organic compound gas of silicon
3)
3) the gas supply source 35 of supply source of steam, be connected with a branched pipe 33a by supply equipment group 34.In addition, as the film forming gas of the processing gas that comprises carbon and fluorine (C for example
5F
8Gas) gas supply source 37 is connected with another branched pipe 33b by supply equipment group 36.Wherein, gas supply equipment group 34 and 36 is contained valve and as mass flow controller of flow adjustment part etc.
In these inscapes, utilize gas supply member 3, gas to supply with road 33, branched pipe 33a, gas supply equipment group 34 and gas supply source 35, and form flow control and first gas supply system of supplying with as the TMS gas of the first processing gas.
As shown in Figure 2, on gas supply member 3, be formed with a plurality of through holes 38 that connect in vertical direction.This through hole 38 is used to make the spike that generates in plasma span S1 to drop in the processing space S 2.Each through hole 38 is formed at contiguous gas flow path 32 each other.
Front with the gas supply road 4 that is communicated with in the plasma span S1 is connected with container handling 1.There is branched pipe 41,42,43 in the base end side branch that this gas is supplied with road 4.Gas supply equipment group 51 is connected with branched pipe 41 with the supply source 52 of rare gas (for example Ar gas).Gas supply equipment group 53 and O
2 Gas supply source 54 is connected with branched pipe 42.Gas supply equipment group 55 is connected with branched pipe 43 with nitrogen supply source 56.Each gas supply equipment group 51,53,55 is contained valve and mass flow controller etc.
In these inscapes, utilize gas supply road 4, branched pipe 43, gas supply equipment group 55 and the 56 formation flow controls of gas supply source and supply second gas supply system as the nitrogen of the second processing gas.
Wherein, the structure as supply gas is not limited to the foregoing description, also can be as following.That is, in gas supply member 3, be provided for C independently
5F
8First gas flow path of gas and TMS gas and be used for oxygen and second gas flow path of nitrogen.In addition, a plurality of gas supply holes 31 are divided into first supply hole that is communicated with first gas flow path and second supply hole that is communicated with second gas flow path.For example, first supply hole and the second gas supply hole dispose alternately.Adopt this structure that is used for supply gas,, can obtain the inner evenness of height for the membranous and thickness of the film that on wafer W, forms.
But above gas supply member 3, be provided with by microwave permeable material (aluminium oxide (Al for example
2O
3) or quartz etc.) dielectric plate (microwave penetrating window) 6 that constitutes.This dielectric plate 6 is provided with antenna 7, and this antenna 7 closely contacts with this dielectric plate 6.As shown in Figure 3, this antenna 7 discoideus planar antenna member (frid) 71 of having discoideus antenna body 70 and being installed in the following side of this antenna body 70.These antenna main body 70 and planar antenna member 71 all are made of conductor, are formed with the waveguide pipe of flattened round between them.In example shown in Figure 1, antenna body 70 is divided into two parts up and down.The inside of parts in its lower section is formed with by the circulate coolant of coolant of the coolant stream from the outside and accumulates portion 72.
For example between planar antenna member 71 and antenna body 70, be provided with the stagnant phase-plate 73 that constitutes by low loss dielectric substances such as aluminium oxide or silica, silicon nitrides.The phase-plate 73 that should stagnate can shorten the wavelength of microwave, and the wavelength in pipe of above-mentioned circular waveguide is shortened.Utilize these antenna main body 70, planar antenna member 71 and stagnant phase-plate 73, and constitute radial line slot antenna (RLSA).
The antenna 7 of Gou Chenging like this, its planar antenna member 71 closely contacts with dielectric plate 6, by the seal member that does not illustrate among the figure, and is installed in the container handling 1.This antenna 7 for example is connected for the microwave generating apparatus 12 of 2.45GHz or 8.4GHz microwave with the supply frequency by coaxial waveguide pipe 11.The outside waveguide pipe 11A of coaxial waveguide pipe 11 is connected with antenna body 70, and center conductor 11B connects stagnant phase-plate 73 and is connected with planar antenna member 71.
As shown in Figure 1, blast pipe 13 is connected with the bottom of container handling 1.Vacuum pump 15 is for example by the pressure adjustment part 14 that is made of butterfly valve etc. and be connected with the base end side of blast pipe 13.In addition, on the inwall of container handling 1, also be provided with the sleeve 17 of imbedding heater 16.
Plasma processing apparatus has the control part 10 of the switch 22 that control gaseous supply equipment group 34,36,51,53,55, pressure adjustment part 14, heater 16, microwave generating apparatus 12 and electrostatic chuck use.This control part 10 has storage part etc., stores to be used to be implemented in the sequential program that the aftermentioned film forming of carrying out in the container handling 1 is handled each operation.
Then, an embodiment who uses the film build method that this device implements is described.
At first, will by the gate valve that does not illustrate among the figure, move into and handle in the container 1, and be placed on the mounting table 2 as the wafer W of substrate.Here, use and to be formed with the interlayer dielectric 81 that the carbon by the fluoridize shown in Fig. 4 (a) constitutes and the wafer W of copper wire 82 in advance from the teeth outwards.
Secondly, the inside with container handling 1 is evacuated to authorized pressure.In addition, supply with road 4, will be supplied to as the Ar gas of plasma gas in the container handling 1 by gas, simultaneously, will be as the C of unstrpped gas
5F
8Gas is supplied with road 33 by gas, is supplied in the container handling 1 from gas supply member 3.To maintain predetermined process pressure in the container handling 1, the surface temperature of mounting table 2 is set at set point of temperature.
On the other hand, when when a microwave generating apparatus 12 is supplied with the microwave of 2000W with 2.45GHz, this microwave transmits in coaxial waveguide pipe 11 with TM pattern, TE pattern and TEM pattern.Arrive the inner conductor 11B of the microwave of antenna 7 by coaxial waveguide pipe 11, the mind-set periphery edge is radial spread from planar antenna member 71.Betwixt, microwave is from each groove 74A, 74B radiation downwards by dielectric plate 6.Because but dielectric plate 6 is to be made by microwave permeable materials such as aluminium oxide, therefore, the microwave of radiation can see through expeditiously.
Utilize the configuration (Fig. 3) of above-mentioned groove 74A, 74B, microwave is emitted as the circle partial wave on the plane of whole planar antenna member 71 equably as the circle partial wave, and the electric field density of the plasma span S1 below making is even.Utilize the energy of this microwave, to high-density the uniform Ar gaseous plasma of excitation in plasma span S1.
This plasma drops in the processing space S 2 of below by the through hole 38 of gas supply member 3.This plasma will be from gas supply member 3 to handling the C that space S 2 is supplied with
5F
8Gas activation and form spike.This spike is deposited on the surface of wafer W, forms thickness and for example is the interlayer dielectric that carbon constituted 91 by fluoridize shown in Fig. 4 of 200nm (a).Promptly, adopt this plasma processing unit, below the plasma span S1 of clamping gas supply member 3, the space S 2 of the processing that the formation spike mainly exists (here, plasma not luminous (plasma emission)), therefore, can be described as the carbon film that utilizes soft (soft) spike to form fluoridize.Because like this, can obtain the carbon film dense and fluoridize that compactness is high, thermal stability is high.
Secondly, do not take out of wafer W, on the interlayer dielectric that carbon constituted 91, form SiCN film and SiCO film continuously by fluoridize from container handling 1.
At first, the film forming to the SiCN film describes.When SiCN film film forming, except activation TMS gas and the plasma that obtains, the spike of essential nitrogen also, and in this embodiment, do not supply with nitrogen during the initial stage in film forming.That is, open each valve of gas supply equipment group 51,34, TMS gas and Ar gas are supplied in the container handling 1, simultaneously, will be maintained processing pressure in the container handling 1.
On the other hand, with the microwave that 2.45GHz supplies with regulation power, encourage plasma from microwave generating apparatus 12 as mentioned above like that.The TMS gas (plasmaization) that utilizes this plasma activation to supply with from gas supply member 3.Like this, produce the spike (plasma) of silicon, carbon and hydrogen, shown in Fig. 4 (b), form 92 (also comprising hydrogen in detail) of SiC (carborundum) film.
For example, after 5 seconds, open gas supply equipment group 55 valve, nitrogen is supplied with road 4 from gas be supplied in the container handling 1 at the initial stage film forming procedure that forms SiC film 92.Like this, generate the spike of nitrogen, shown in Fig. 4 (c), on SiC film 92, form SiCN film 93.The total thickness of SiC film 92 and SiCN film 93 for example is 5nm.The SiCN film is for for example containing the silicon carbide film of 10 atom % nitrogen.
Then, in one operation of back, form the SiCO film that uses as hard mask.In this film forming procedure, the TMS gas setting of supplying with during for example with SiCN film 93 film forming is the flow of SiCO film film forming scheme and continues to flow, meanwhile, close gas supply equipment group 55 valve, stop the supply of nitrogen, open gas supply equipment group 54 valve, begin oxygen is supplied in the container handling 1.Then, will be maintained predetermined processing pressure in the container handling 1, and supply with microwave, activation TMS G﹠O, excitation plasma from microwave generating apparatus 12.Shown in Fig. 4 (d), utilizing this plasma to form thickness for example is the SiCO film 94 of the conduct first hard mask about 50nm.This SiCO film is for example for containing the silicon carbide film of 20 atom % oxygen.
Wherein, the film formation process of SiCO film 94 is not supplied with oxygen in film forming during the initial stage, only make TMS gas for example flow through 5 seconds, then, when adding oxygen in TMS gas, can further improve the compactness of 94 pairs of SiCN films 93 of SiCO film.
Secondly, shown in Fig. 4 (e), on SiCO film 94, form the film of using by the second hard mask of the material different (being silica here) formation 95 with SiCO.This film formation process for example also can be by using the steam and the oxygen in organic source such as TEOS in the device of Fig. 1, activate these gases and obtain plasma and implement, and perhaps also can utilize other film formation device to implement.Then, though do not illustrate among the figure, on silicon oxide film 95, be formed with the resist film of certain figure.Come etching oxidation silicon fiml 95 with this resist film as mask, then, Etching mask is removed in ashing.Like this, obtain having the second hard mask 95 (Fig. 4 (f)) with the corresponding figure of resist film figure.
Then, on the surface of wafer W, form resist film 96 (Fig. 5 (g)) with width figure narrower than the figure of the second hard mask 95.As mask, utilize the plasma of the spike that for example contains halogen compounds to come etching SiCO film 94 with this resist film 96, then, Etching mask 96 is removed in ashing.Like this, obtain having the first hard mask 94 with the corresponding figure of figure of resist film 96.Utilize this first hard mask, for example come the carbon film 91 (Fig. 5 (h)) of etching fluoridize by oxygen plasma.Wherein, on the surface of substrate layer 81,82, in fact have barrier layer or hard mask, but for convenience, and in Fig. 4 with its omission.
And, utilize the second hard mask 95 that constitutes by silica, connect etching SiCN film 93 and SiCO film 94 in the time of (comprising SiC film 92), be etched to the centre of the carbon film 91 of fluoridize.Like this, form the big recess (Fig. 5 (i)) of recess that width forms than previous etching.Wherein, the narrow recess of width that forms on the carbon film 91 of fluoridize is equivalent to via hole, and the wide recess of the width on it is equivalent to imbed the zone of return lead.Then, shown in Fig. 6 (j), will be embedded in as the copper 97 of circuit metal recess all in.Then, for example remove, form copper wire 97 (Fig. 6 (k)) by the grinding that is called CMP (chemico-mechanical polishing) from the part copper that recess exposes.Then, though do not illustrate among the figure, be formed with SiC layer as barrier layer etc. from the teeth outwards.
According to above execution mode, when forming the SiCO film 94 that hard mask uses on the carbon film 91 at fluoridize, being situated between as diaphragm is having SiCN film 93.Therefore, employed oxygen activity kind has obstruction to SiCN film 93 when the film forming of SiCO film 94, can suppress the reaction with the carbon of the carbon film 91 of fluoridize.Therefore, reduce the degassing scale of construction of the carbon film 91 of fluoridize.
In addition, when the SiCN film 93 that forms as diaphragm, the surface ratio nitrogen plasma of the carbon film 91 of fluoridize is exposed to earlier in the plasma atmosphere of TMS gas.Because (such described in " embodiment " as described later) like this, the compactness of the carbon film 91 of SiCN film 93 and fluoridize becomes.In addition, SiCN film 93 and SiCO film 94 is because make substrate for identical carborundum, so both compactnesses are big.As a result, can obtain bigger compactness between the carbon film 91 of SiCO film 94 and fluoridize.Therefore, can use the SiCO film as hard mask.
The surface ratio nitrogen plasma of the carbon film 91 of fluoridize is exposed to earlier in the TMS gaseous plasma atmosphere, and the reason that can make the compactness of SiCN film 93 become good is also not fully aware of.(but as described later described in " reference example " like that), think that the enriched carbon layer that forms on the surface of the carbon film 91 of fluoridize may not collect nitrogen.As a result, can avoid nitrogen to overflow from the carbon film of fluoridize, the density of film is reduced, and the compactness that causes be bad as gas.
In the present embodiment, the gas as producing plasma except Ar gas, can also use for example rare gas such as He (helium) gas, Ne (neon) gas, Kr (krypton) gas, Xe (xenon) gas.In addition, the purposes as the carbon film of fluoridize just is not limited to interlayer dielectric, for example can be other dielectric films yet.And, be not only limited to C as the unstrpped gas of the carbon film of fluoridize yet
5F
8Gas for example also can use CF
4Gas, C
2F
6Gas, C
3F
8Gas and C
4F
8Gas etc.
In addition, as when forming SiCN film 93, being used to obtain the gas of the spike of nitrogen, is not to only limit to nitrogen, can be ammonia yet.
In addition, the organic compound of employed silicon is not limited in TMS gas during as formation SiCN film 93 or SiCO film 94, also can be other organic compounds.Object lesson has: CH
3SiH
3, (CH
3)
2SiH
2, (CH
3)
3SiH, (CH
3)
4Si, (CH
3)
2Si (OC
2H
5)
2, (CH
3)
2Si (OCH
3)
2, CH
3Si (OC
2H
5)
3, CH
3Si (OCH
3)
3, (HCH
3SiO)
4[circulus], ((CH
3)
3Si)
2O, (H (CH
3)
2Si)
2O, (H
2CH
3Si)
2O, ((CH
3)
2SiO)
3, (CH
3ASiO)
3, ((CH
3)
2SiO)
4, (CH
3ASiO)
4Deng.Last three kinds of compounds are circulus, and " A " is vinyl (CH-CH
3).
Secondly, second execution mode of the present invention is described.This execution mode is to use the method for SiCN self as hard mask.Specifically, the film of using as the first hard mask with SiCN film self forms the film of being used by the second hard mask that constitutes with SiCN film unlike material on this film.Therefore, the thickness of SiCN film for example is 50nm, and its method for making and above-mentioned first execution mode are identical.That is, during the initial stage, do not supply with nitrogen, only supply with TMS gas and Ar gas, then, except that these gases, also supply with nitrogen in the film forming of SiCN film.If described corresponding with Fig. 4～Fig. 6, then SiCN film 93 and SiCO film 94 film altogether are equivalent to the SiCN film of the film used as the first hard mask.In this case, the second hard mask becomes silicon oxide film, also can replace it with the SiCO film.
Adopt this execution mode, as mentioned above, utilize the enriched carbon layer form on the carbon film surface of fluoridize to collect nitrogen, then, because few from the degassing scale of construction of the carbon film of fluoridize, the compactness between the carbon film of SiCN film and fluoridize becomes fabulous.
In above each execution mode, for carbon film, SiCN film and the SiCO film that forms fluoridize, and use single container handling 1, but also can use three container handlings, carry out film forming respectively.In this case, each container handling is connected with common vacuum conveyance container, by the conveyance container, conveyance substrate between each container handling successively.Perhaps, also three container handlings can be connected in series, by separating load locking chamber, the conveyance substrate successively between each container handling.And, also can use same container handling to form two films in carbon film, SiCN film and the SiCO film of fluoridize, use another container handling to form remaining film.In addition, also can not utilize plasma processing apparatus, but utilize the processing unit that for example splashes to form the SiCN film.
Secondly, the 3rd execution mode of the present invention is described.
This execution mode can obtain semiconductor device shown in Figure 7.In this semiconductor device, on the SiCO film 41 of the part of the interlayer dielectric that constitutes porous materialization, form SiCN film 42 as diaphragm.Then, on this SiCN film 42, form carbon film 40 as the fluoridize of interlayer dielectric.That is, the carbon film 40 of SiCO film 41 and fluoridize, clamping SiCN film 42 forms as double-deck interlayer dielectric.Wherein, this interlayer dielectric 41,40 is stacked to be formed at circuit and to imbed on the structure division in thereunder the interlayer dielectric, constitutes the part of sandwich construction circuit.
On this interlayer dielectric 41,40, be formed with recess 48.When seeing in the cross section at Fig. 7, this recess 48 is formed by the expansion recess 48b (groove that circuit is used) that forms on narrow and small recess 48a (being equivalent to via hole) that forms on the SiCO film 41 and the carbon film 40 at fluoridize.In this recess 48, for example imbed copper 47 as line layer.In addition, on the carbon film 40 of fluoridize, be formed with SiCN film 43 as diaphragm.On this SiCN film 43, the SiO of the film of using by the hard mask of the residual a little conduct of the grinding step that is called CMP as described later
2 Film 44.
Then, according to Fig. 8, the manufacturing process of semiconductor device shown in Figure 7 is described.This semiconductor device can utilize according to the plasma treatment of Fig. 1～Fig. 3 explanation and implement.In this example, use the wafer W that is pre-formed the substrate layer that constitutes by interlayer dielectric and circuit from the teeth outwards.
At first, shown in Fig. 8 (a), on the substrate layer of wafer W, form the SiCO film 41 of porous materialization and as the SiCN42 of diaphragm.The film forming of the SiCO film 41 of porous materialization now is described.At first, Ar gas and TMs gas are supplied in the container handling 1, as mentioned above, utilize the plasma of excitation to form the SiCH film.Then, utilize the plasma that obtains at container handling 1 activation oxygen, with the CH in the SiCH film
3Base is replaced into O, become in conjunction with grid little, the SiCO film 41 of porous materialization.The film thickness of this SiCO film 41 for example is about 100nm.This SiCO film 41 is for for example containing the silicon carbide film of 20 atom % oxygen.Like this, become porous matter by making SiCO film 41, the dielectric constant of SiCO film 41 drops to 2.2 from 3.0.Because like this, carbon film 40 combinations of utilization and fluoridize, and, can form the low dielectric film of all dielectric constants as double-deck interlayer dielectric.
Secondly, as mentioned above, on SiCO film 41, form SiCO film 42, afterwards, shown in figure (b), form the carbon film 40 of fluoridize thereon.This film forming procedure is identical with the film forming procedure of the carbon film 91 of the fluoridize of first execution mode.The thickness of the carbon film 40 of this fluoridize for example is approximately about 100nm.Shown in Fig. 8 (c), on the carbon film 40 of fluoridize, form SiCN film 43.This film forming procedure is identical with the film forming procedure of SiCN film 42.The thickness of these SiCN films 42,43 for example is approximately about 5nm.
At this moment, as described in first execution mode, the SiCN film 43 on upper strata also can make the stepped construction of SiC film 92 and SiCN film 93.
In addition, shown in Fig. 8 (d), on SiCN film 43, form the film SiO that hard mask is used
2Film 44.This film forming is to utilize the plasma encourage for example silane gas and oxygen and to obtain formed.Then, at SiO
2Form Si on the film 44
3N
4Film 45 forms thereon with TEOS and O
2Make the SiO of raw material
2Film 46.Si
3N
4The thickness of film 45 for example is approximately about 50nm, SiO
2The thickness of film 46 for example is approximately about 50nm.Then, though do not illustrate among the figure, at SiO
2Be formed with resist film on the film 46 with certain figure.By carrying out etching as mask with this resist film, and at SiO
2Film 46 and Si
3N
4Form figure graph of a correspondence on the film 45 with resist film.
Shown in Fig. 8 (e), SiO
2The figure of film 46 therein near the heart etching width L2, Si
3N
4The figure of film 45 therein near the heart etching width L1 littler than width L2.Utilize these two figures of these width L2, L1 to carry out etching, and form recess shown in dotted line.Then, shown in Fig. 8 (f), in the recess that forms by etching, imbed copper 47 as the circuit metal.Then, the part copper 47 that utilizes the CMP operation to remove to expose from recess 48 is to SiO
2The centre of film 44 obtains structure shown in Figure 7.
Adopt the following effect of having of this execution mode, in the present embodiment,, use the combination of the CF film (organic system) 40 and the SiCO film (inorganic system) 41 of different kind as interlayer dielectric.Therefore, behind the dotted portion in the L1 zone of etch figures(s) 8 (e), when the dotted portion in etching L2 zone, during the CF of etching organic system film 40, the side of the SiCO film 41 of the inorganic system of not etching.The shape that can suitably keep like this, via hole 48a.In addition, if C-F combination and Si-O in conjunction with vicinity, then when annealing, might become SiF
4And be easy to the problem of different China.And, as present embodiment, utilize SiCN film 42 physically to separate between carbon 40 films of SiCO film 41 and fluoridize, and can address this problem as diaphragm.And in the present embodiment, after forming recess 48, when the copper 47 imbedded as line layer, wafer W temporarily can be exposed in the atmosphere.At this moment, because SiCO film 41 is made porous matter, so absorb moisture etc. easily.In this case, if there is not a SiCN film 42, then, and make the carbon film 40 of fluoridize become CO or HF causes dispersing, natural wastage because the water that is absorbed by SiCO film 41 enters in the carbon film 40 of fluoridize.By between SiCO film 41 and CF film 40, placing SiCN film 42, immerse in the carbon film 40 of fluoridize and can stop by the moisture of SiCO film 41 absorptions.In addition, the SiCN film 43 on the carbon film 40 of fluoridize plays prevention at SiO
2The oxygen atomic group that uses in the film forming of film 44 is to the effect of the destruction of the carbon film 40 of fluoridize.
As mentioned above, the carbon film of fluoridize is the dielectric film with good characteristic, but it also has the destruction that caused by oxygen, nitrogen, moisture etc. and rotten shortcoming.On the other hand, when making semiconductor element, to consider also that all the interlayer dielectric with the carbon film processing multilayer of fluoridize is very difficult.In this case, the Si oxide insulating film that can consider to use all the year round, be the dielectric film that the carbon film of stacked SiOX film (X is arbitrary element, compound) and fluoridize constitutes, but have following point this moment.
Below 400 ℃ the time, avoid in film, forming trace and SiOH structure at the film-forming temperature of SiOX film.The SiOH structure in the operation after film forming, carries out cutting off the OH base under annealing operation more than 400 ℃ (for example sintering etc.) situation, and its part moves to the interface with the carbon film of fluoridize.Like this, further reaction and generate SiF of the F of the carbon film of fluoridize and OH radical reaction and generate HF, HF and SiOX film
4And then the compactness of the carbon film of fluoridize and SiOX film reduces.Producing these films peels off each other.
In order to address this problem, also can be at the SiO of the SiCO of first execution mode film 94, the 3rd execution mode
2Between the SiOX film that film 44, SiCO film 41 are such and the carbon film of fluoridize, as thin as a wafer SiCN film among clamping the present invention.Wherein, SiCN film described here as described in first execution mode, is the object of the stepped construction that comprises SiC film 92 and SiCN film 93.The carbon film of SiCN film and fluoridize relatively, it has 4.5 high value than dielectric constant, does it as thin as a wafer, can suppress the rising of total ratio dielectric constant.For example, the carbon film of the fluoridize of 100nm respectively form the dielectric film that thickness is the SiCN film of 5nm up and down, its all ratio dielectric constant is 2.3.Therefore, be 2.2 with respect to the ratio dielectric constant of the carbon film monomer of fluoridize, its rising is very little, can play the effect of low-down k (Low-k) film.Here, the destruction that so-called " as thin as a wafer " expression can be prevented block, nitrogen, moisture etc. reaches the thin of degree that the ratio dielectric constant that can suppress total rises.Thickness is 3～10nm, is preferably 5～8nm.And, as the material of insulant as thin as a wafer, also can use SiC (carborundum), SiN (silicon nitride), agraphitic carbon to wait and replace SiCN.
Below, the specific embodiment corresponding with above-mentioned first～the 3rd execution mode described.
The film forming of the film that A. hard mask is used
(embodiment 1)
This embodiment 1 is corresponding with second execution mode.Use plasma processing apparatus shown in Figure 1, forming thickness on the naked wafer of silicon is the carbon film of the fluoridize of 120nm.Membrance casting condition is set at: microwave power is that 3000W, processing pressure are that 10.6Pa (80mTorr), chip temperature are 380 ℃, C
5F
8The flow of gas and Ar gas is respectively 200sccm and 100sccm.
Secondly, utilize the same plasma processing unit, on the carbon film of fluoridize, forming thickness is the SiCN film of 50nm.Membrance casting condition is set at: microwave power is that 1500W, processing pressure are that 39.9Pa (300mTorr), chip temperature are 380 ℃.In addition, supply with TMS gas (steam) and Ar gas with the flow of 40sccm and 800sccm respectively, simultaneously, after supplying with TMS gas and Ar gas certainly and beginning 5 seconds, with the flow supply nitrogen of 50sccm.
(embodiment 2)
This embodiment 2 is corresponding with first execution mode.Identical with first execution mode, on the naked wafer of silicon, form the carbon film and the SiCN film of fluoridize successively.But, in this example, because the SiCN film plays the protective layer effect, so its thickness is 5nm.Secondly, utilize identical plasma processing apparatus, forming thickness on the SiCN film is the SiCO film of 50nm.Membrance casting condition is set at: microwave power is that 1500W, processing pressure are that 33.3Pa (250mTorr), chip temperature are 380 ℃.In addition, supply with TMS gas and Ar gas with the flow of 40sccm and 200sccm respectively, simultaneously, begin to supply with TMS gas and Ar gas certainly after 5 seconds, supply with nitrogen with the flow of 10sccm.
(embodiment 3)
Identical with embodiment 2, on the carbon film of fluoridize, press this sequential cascade SiCN film and SiCO film.But, when forming the SiCN film, be not the operation of only supplying with TMS gas and Ar gas in film forming during the initial stage, from just supplying with TMS gas, Ar gas and nitrogen at first.
(comparative example 1)
Identical with embodiment 1, stacked SiCN film on the carbon film of fluoridize.But, as different from Example 1, when forming the SiCN film, be not the operation of only supplying with TMS gas and Ar gas in film forming during the initial stage, but just supply with TMS gas, Ar gas and nitrogen with this flow from initial.
(comparative example 2)
Identical with embodiment 2, obtain duplexer.As different from Example 2, on the carbon film of fluoridize, do not form the SiCN film, but directly form the SiCO film.
B. the investigation of film compactness
In vacuum atmosphere, the wafer to 400 of heating embodiment 1～3 and comparative example 1,2 ℃, and placed 30～60 minutes.Then, by the surface of each wafer of perusal, whether peel off with splicing tape research again.
Like this, in the wafer of comparative example 1, more or less can see based on the transition interval that from film, produces bubble (blister: bubble), have small part generation film to peel off in addition.Relative therewith, in the wafer of embodiment 1, can't see the transition interval of comparative example 1 fully, there be not peeling off of film fully.Therefore, as can be seen,, during the initial stage, only do not supply with TMS gas and Ar gas, make the SiCN film increase with respect to the compactness of the carbon film of fluoridize by not supplying with nitrogen in film forming forming under the situation of SiCN film on the carbon film of fluoridize.
In addition, in the wafer of embodiment 2, cannot see above-mentioned transition interval fully, and do not have peeling off of film fully.This is because the film build method of SiCN film is identical with embodiment 1, SiCO film and SiCN film all with SiC as substrate, may be described as incorporate film, be considered to natural result.
In addition, when investigating the concerning of embodiment 3 and comparative example 2, embodiment 3 be the result identical with comparative example 1, still compares outstanding with comparative example 2.That is, in comparative example 2, the above-mentioned transition interval of seeing is than embodiment more than 3, and most film is peeled off.Thus, as can be seen, embodiment 3 compares with comparative example 2, the compactness height of its film.Therefore, as can be seen, when the SiCO film is used as hard mask, preferably between the carbon film of fluoridize and SiCO film, put into the SiCN film.In addition, as can be seen, more preferably SiCN film film forming adopted in film forming during the initial stage, did not supply with nitrogen and only supplied with the method for TMS gas and Ar gas.
C. reference experiment
In the duplexer of embodiment 1, utilize SIMS (secondary ion mass spectrometry device), be index with secondary ion intensity, the carbon of research depth direction and the concentration of nitrogen obtain the result shown in Fig. 9 (a).On the other hand, in embodiment 1, before supplying with TMS gas and Ar gas, the carbon film of fluoridize is exposed in the nitrogen gas plasma 60 seconds, the duplexer that same research obtains obtains the result shown in Fig. 9 (b).
In Fig. 9 (a), can see the high position of carbon and nitrogen concentration (in the circle of dotted line) on the interface of the SiCN film suitable and the carbon film of fluoridize with degree of depth 50nm.In addition, the nitrogen concentration in the carbon film of fluoridize was reduced to below 1 from reduce with the interface of SiCN film is anxious sharply in maximum 10 minutes.On the other hand, in Fig. 9 (b), can't see the such tendency of Fig. 9 (a).
From this results presumption, about the compactness of SiCN film to the fluoridize carbon film, when SiCN film film forming, nitrogen invades in the carbon film of fluoridize, and nitrogen is emitted as breaking away from gas during heating, and compactness does not reduce.Relative therewith, when film forming as embodiment 1, on the interface, form the many zones of concentration of carbon and can be described as enriched carbon layer.Then, this enriched carbon layer is collected wafer is exposed to nitrogen in the nitrogen plasma, can prevent to invade in the carbon film of fluoridize, and result, the compactness of SiCN film may not be very big.
Claims (8)
1. the manufacture method of a semiconductor device is characterized in that, comprising:
On substrate, form operation by the dielectric film that carbon constituted of fluoridize;
On described dielectric film, form the operation of the protective layer that contains the silicon carbide film formation that adds nitrogen; And
Utilization contains the plasma of the spike of silicon, carbon and oxygen, forms the operation that carborundum by oxygenation constitutes the film that hard mask uses on described protective layer.
2. the method for claim 1 is characterized in that:
Contain the plasma that the described plasma of the spike of silicon, carbon and oxygen obtains for gas and oxygen activation with the organic compound of silicon.
3. the method for claim 1 is characterized in that,
The operation that forms described protective layer comprises:
Utilization contains the plasma of the spike of silicon and carbon, forms the auxiliary process of silicon carbide film on described dielectric film; And
Utilization contains the plasma of the spike of silicon, carbon and nitrogen, forms the auxiliary process of the silicon carbide film that adds nitrogen on described silicon carbide film.
4. the method for claim 1 is characterized in that,
The operation that forms described protective layer comprises:
The plasma that utilization obtains the activation of the organic compound gas of silicon forms the auxiliary process of silicon carbide film on described dielectric film; And
Utilization contains the plasma of the spike of the spike of organic compound of silicon and nitrogen, forms the auxiliary process of the silicon carbide film that adds nitrogen on described silicon carbide film.
5. the method for claim 1 is characterized in that, also comprises:
On the film that described hard mask is used, form the operation of resist film with certain figure;
By described resist film, utilize the described film of plasma etching, obtain having operation with the hard mask of the figure graph of a correspondence of described resist film; With
By described hard mask, utilize the operation of the described dielectric film of plasma etching.
6. the manufacture method of a semiconductor device is characterized in that, comprising:
On substrate, form the operation of the dielectric film that the carbon by fluoridize constitutes;
Utilization contains the plasma of the spike of silicon and carbon, forms the operation of silicon carbide film on described dielectric film; And
Utilization contains the plasma of the spike of silicon, carbon and nitrogen, the operation of the film that the hard mask that formation is made of the carborundum that adds nitrogen on described silicon carbide film is used.
7. method as claimed in claim 6 is characterized in that:
The described plasma that contains the spike of silicon and carbon obtains plasma for the organic compound gas activation with silicon.
8. method as claimed in claim 6 is characterized in that:
Contain the plasma that the described plasma of the spike of silicon, carbon and nitrogen obtains for gas and nitrogen activation with the organic compound of silicon.
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| US8197913B2 (en) * | 2007-07-25 | 2012-06-12 | Tokyo Electron Limited | Film forming method for a semiconductor |
| KR101413380B1 (en) * | 2007-08-28 | 2014-06-30 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Method for manufacturing semiconductor die and a semiconductor device comprising the semiconductor die obtained thereby |
| JP5772508B2 (en) * | 2011-10-27 | 2015-09-02 | 東京エレクトロン株式会社 | Film forming apparatus and operation method thereof |
| CN104425222B (en) * | 2013-08-28 | 2018-09-07 | 中芯国际集成电路制造(上海)有限公司 | Graphic method |
| CN104157790B (en) | 2014-06-30 | 2017-03-15 | 上海天马有机发光显示技术有限公司 | A kind of organic light emitting film encapsulating structure, its device, device and manufacture method |
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