CN104134630B - A kind of method for reducing side wall damage of ultralow dielectric constant film - Google Patents
A kind of method for reducing side wall damage of ultralow dielectric constant film Download PDFInfo
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- CN104134630B CN104134630B CN201410411972.XA CN201410411972A CN104134630B CN 104134630 B CN104134630 B CN 104134630B CN 201410411972 A CN201410411972 A CN 201410411972A CN 104134630 B CN104134630 B CN 104134630B
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- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76822—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc.
- H01L21/76826—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc. by contacting the layer with gases, liquids or plasmas
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/10—Applying interconnections to be used for carrying current between separate components within a device
- H01L2221/1005—Formation and after-treatment of dielectrics
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Abstract
The present invention provides a kind of method for reducing side wall damage of ultralow dielectric constant film, including：Step S01：Dielectric barrier layer and the low-dielectric constant layer containing pore-foaming agent are sequentially depositing on a semiconductor substrate；Step S02：It is passed through carbonaceous gas and corona treatment is carried out to low-k layer surface；Step S03：Remove pore-foaming agent；Step S04：Dielectric barrier layer and metal hard mask layer are sequentially formed in low-k layer surface；Step S05：The metal hard mask layer, dielectric barrier layer, carbon containing oxide layer and low-dielectric constant layer are performed etching, to form groove.The present invention is passed through carbonaceous gas and carries out corona treatment to low-dielectric constant layer, the carbon of incorporation makes etch rate of the carbon containing oxide layer in chemical solution close to the etch rate of low-dielectric constant layer, so as to avoid the side wall of groove structure from being recessed, in addition, incorporation carbon can also reduce the dielectric constant values of film, improve the electric property of device.
Description
Technical field
The present invention relates to semiconductor integrated circuit and its manufacture field, more particularly to a kind of ultralow dielectric constant film of reduction
The method of sidewall damage.
Background technology
Improved constantly with the integrated level of integrated circuit, semiconductor technology is also lasting to be developed rapidly.In semiconductor manufacturing
In technique, because aluminum interconnecting has good electric conductivity, and have between aluminium and dielectric material, semi-conducting material fine
Adhesion property, so be widely used in integrated circuit back segment interconnection；However, with the further raising of integrated level,
So that the size of wire is less and less, and the resistance of aluminum conductor just seems higher, has been difficult to the requirement for meeting high current density,
Therefore aluminum interconnecting is gradually transitions copper conductor.
In addition, by the use of dielectric layer with low dielectric constant as dielectric layer between metal layers, can effectively reduce electric capacity.Copper-connection skill
The dielectric layer between metal layers (intermetal dielectric, IMD) that are constituted of art collocation advanced low-k materials are at present most
Welcome interconnection structure process combination, it can be effectively improved the phenomenon of RC delays, and it will turn into the next generation and partly lead
One of standardized interconnection technology of body technology.
In integrated circuit technology, ultralow dielectric constant material must is fulfilled for all many conditions, for example：Enough mechanical strengths
To support the framework of multilayer interconnection, high young's modulus, high-breakdown-voltage, Low dark curient, high thermal stability, good bonding strength,
Compatibility of low water absorbable, low membrane stress, high planarization capability, low-heat coefficient and CMP process etc..
The method of the existing ultralow dielectric constant film of formation is at present：Step S01, deposits be situated between over the semiconductor substrate 10
Electrical barrier 20 and the low-dielectric constant layer 30 (as shown in Figure 1) containing pore-foaming agent 40；Step S02, to low-dielectric constant layer
30 surfaces carry out oxygen gas plasma processing, to remove the reactant predecessor of the remained on surface of low-dielectric constant layer 30, and low
The surface of dielectric constant layer 30 forms oxide layer 50 (as shown in Figure 2)；Step S03, removes the pore-foaming agent in low-dielectric constant layer 30
40, to form the low-dielectric constant layer 30 (as shown in Figure 3) of micropore；Step S04, the surface of low-dielectric constant layer 30 after treatment
Sequentially form dielectric barrier layer 20 and metal hard mask layer 60 (as shown in Figure 4)；Step S05：Using etching technics in institute
State in metal hard mask layer 60, dielectric barrier layer 20, oxide layer 50 and the formed layer stack structure of low-dielectric constant layer 30 and formed
Groove 70 (as shown in Figure 5)；Step S06：The filling metallic copper in groove 70, the metallic copper fills up groove 70 and covering groove
The metal hard mask layer 60 of 70 both sides；Step S07：It is flat to the metallic copper and above-mentioned stepped construction using cmp
Smoothization, to exposing the low-dielectric constant layer 30.
But, remove the reactant forerunner remained in reaction chamber due to being handled using oxygen gas plasma in the above method
Thing, can cause film surface to form one layer of relatively compact oxide layer, subsequently using the process of chemical solution etching groove
In, because etch rate of the oxide layer in chemical solution is typically larger than the etch rate of low-dielectric constant layer, so as to cause ditch
Often there is concave curved pattern (refer to Fig. 5), i.e. the side wall relative to low-dielectric constant layer 30, oxide layer in the side wall of the structure of groove 70
50 side walls collapse is often relatively deep, so that depression 80 occurs in the side wall of the structure of groove 70, the presence of depression 80 can influence subsequently
Manufacturing process, such as in follow-up copper fill process, easily form the defect such as copper filling hole.Therefore it provides one kind subtracts
The method of few side wall damage of ultralow dielectric constant film turns into those skilled in the art's urgent problem to be solved.
The content of the invention
It is an object of the invention to provide a kind of method for reducing side wall damage of ultralow dielectric constant film, it can repair super
Harmful effect caused by the sidewall damage that low dielectric constant film is brought due to etching, keeps the side of the groove structure after etching
Wall is planarized, while the technique can make the K values of dielectric constant relatively low.
To solve the above problems, the present invention provides a kind of method for reducing side wall damage of ultralow dielectric constant film, including：
Step S01：Dielectric barrier layer and low-dielectric constant layer are sequentially depositing on a semiconductor substrate, wherein, it is described low
Dielectric constant layer contains pore-foaming agent；
Step S02：It is passed through carbonaceous gas and corona treatment is carried out to the low-k layer surface, it is described to remove
The reactant of low-k layer surface, and form carbon containing oxide layer in the low-k layer surface；
Step S03：UV treatment or heating are carried out to the low-dielectric constant layer, to remove the pore-foaming agent；
Step S04：Low-k layer surface after treatment sequentially forms dielectric barrier layer and metal hard mask
Layer；
Step S05：Using etching technics in the metal hard mask layer, dielectric barrier layer, carbon containing oxide layer and low Jie
Groove is formed in permittivity layers the formed layer stack structure.
It is preferred that, the carbonaceous gas is O2With CO2Mixed gas or pure CO2Gas.
It is preferred that, the pressure needed for the carbonaceous gas handles the low-dielectric constant layer is 2~10 supports, and power is 300
~1500W, gas flow is 100~2000sccm, and processing time is 2s~20s.
It is preferred that, the carbonaceous gas also includes inert gas.
It is preferred that, the inert gas is helium, argon gas, nitrogen, nitrogen fluoride or carbon tetrafluoride one or more therein
Combination.
It is preferred that, mix carbon to the low-dielectric constant layer.
It is preferred that, the method for incorporation carbon is ion implanting or plasma doping.
It is preferred that, the low-dielectric constant layer using plasma chemical vapor deposition or spin coating-gel method are formed, institute
The dielectric constant for stating low-dielectric constant layer is 2.2-2.8.
It is preferred that, the material of the metal hard mask layer is Ta or Ti or W or TaN or TiN or WN.
It is preferred that, the material of the dielectric barrier layer in the step S1 is SiN or SiCN.
It can be seen from the above technical proposal that the method for the reduction side wall damage of ultralow dielectric constant film that the present invention is provided
In, it is passed through carbonaceous gas and corona treatment is carried out to the low-k layer surface, the carbon of incorporation makes to contain oxidation of coal
Etch rate of the layer in chemical solution close to low-dielectric constant layer etch rate, so as to avoid the side wall of groove structure from occurring
Concave curved pattern, makes the trenched side-wall after etching keep planarization, in addition, incorporation carbon can also reduce the normal film of low dielectric
Dielectric constant values, the method that the present invention is provided is easily achieved, and the treatment effect of low-dielectric constant layer is more notable, improves device
The electric property of part.
Brief description of the drawings
Fig. 1 to Fig. 5 is formed the cross-section structure of low-dielectric constant layer by the existing method for forming ultralow dielectric constant film
Schematic diagram.
Fig. 6 reduces the flow signal of one embodiment of method of side wall damage of ultralow dielectric constant film for the present invention
Figure；
Fig. 7 to Figure 11 is reduced for the present invention formed in method one embodiment of side wall damage of ultralow dielectric constant film
The cross-sectional view of low-dielectric constant layer.
Embodiment
To make present disclosure more clear understandable, below in conjunction with Figure of description, present disclosure is made into one
Walk explanation.Certainly the invention is not limited in the specific embodiment, the general replacement known to those skilled in the art
Cover within the scope of the present invention.Secondly, the present invention has carried out detailed statement using schematic diagram, real the present invention is described in detail
During example, for convenience of description, schematic diagram, should not be in this, as limitation of the invention not according to general ratio partial enlargement.
Above and other technical characteristic and beneficial effect, by conjunction with the embodiments and accompanying drawing 6 to Figure 11 to the present invention reduction
The method of side wall damage of ultralow dielectric constant film is described in detail.Fig. 6 reduces ultralow dielectric constant film side for the present invention
The schematic flow sheet of one preferred embodiment of the method for wall damage；Fig. 7~11 is are formed using forming method shown in Fig. 6
The schematic diagram of low-dielectric constant layer.
Referring to Fig. 6, in the present embodiment, the present invention provides a kind of side for reducing side wall damage of ultralow dielectric constant film
Method specifically includes following steps：
Step S01：Dielectric barrier layer 20 and low-dielectric constant layer 30 are sequentially depositing over the semiconductor substrate 10, wherein,
The low-dielectric constant layer 30 contains pore-foaming agent 40 (as shown in Figure 7).
Wherein, the material of Semiconductor substrate 10 is monocrystalline silicon, can be that silicon, germanium silicon can also be other semi-conducting materials,
It will not be repeated here.
Specifically, in the present embodiment, the material of dielectric barrier layer 20 can be, but not limited to SiN or SiCN, and low dielectric is normal
Several layers 30 are preferably the silicon oxide layer containing pore-foaming agent 40, and the dielectric barrier layer 20 or low-dielectric constant layer 30 can be used
Existing plasma activated chemical vapour deposition or spin coating-gel growth, the dielectric constant of the low-dielectric constant layer are preferred
For 2.2-2.8, parameter such as pressure, reaction gas flow, temperature etc. employed in forming process can be according to actual process
It is required that to set.Deposition process includes the introducing of pore-foaming agent 40, and pore-foaming agent 40 is organic matter, mainly has carbon and hydrogen to constitute, ultraviolet
Line irradiates or can be dissociated after heating and volatilize to form cavity, so as to reduce the dielectric constant values of low-dielectric constant layer 30.
Step S02：It is passed through carbonaceous gas and corona treatment is carried out to the surface of low-dielectric constant layer 30, removes
The reactant on the surface of low-dielectric constant layer 30 is stated, and carbon containing (such as Fig. 8 of oxide layer 50 is formed on the surface of low-dielectric constant layer 30
It is shown).
Plasma is the 4th state of material, be by part electronics be deprived of after atom and atom be ionized after produce
The vaporous material of ionization of positron-electron composition, this ionized gas is that, by atom, molecule, atomic group, ion, electronics is constituted,
By electric field action, they collide and form plasma, and the activity of these ions is very high, and its energy is enough to destroy almost institute
Some chemical bonds, chemical reaction is caused on the surface of any exposure, and the plasma of gas with various has different chemical properties,
Such as existing oxygen gas plasma, it has very high oxidisability, photoresist reaction generation gas can be aoxidized, so as to reach cleaning
Effect.But oxide layer 50 can be formed on the surface of low-dielectric constant layer 30 by being passed through after oxygen, and oxide layer 50 and low-k
Etch rate of the layer 30 in chemical solution is different, causes the side wall of groove 70 in successive process to produce depression 80 (such as Fig. 5 institutes
Show).
Specifically, in the present embodiment, the carbonaceous gas can be, but not limited to O2 and CO2 mixed gas or pure CO2 gas
Body, the pressure needed for the carbonaceous gas processing low-dielectric constant layer 30 is 2~10 supports, and power is 300~1500W, gas stream
Measure as 100~2000sccm, processing time is 2s~20s.Carbonaceous gas is passed through to carry out the surface of low-dielectric constant layer 30
Corona treatment, the carbon of incorporation can make etch rate of the carbon containing oxide layer 50 in chemical solution normal close to low dielectric
Several layers 30 of etch rate, and the dielectric constant values of carbon containing oxide layer 50 are reduced, improve the electric property of semiconductor devices.
In order to further reduce etch rate of the carbon containing oxide layer 50 in chemical solution, make carbon containing oxide layer 50 with it is described
The etch rate of low-dielectric constant layer 30 is consistent, and carbonaceous gas can also include inert gas, and the inert gas can be with
But it is not limited to helium, argon gas, nitrogen, nitrogen fluoride or carbon tetrafluoride one or more of combination therein.
In the present embodiment, carbon can also be mixed to the low-dielectric constant layer 30, wherein, mix the side of carbon
Method can be ion implanting either plasma doping, wherein, carbon can be carbon atom or carbon containing molecule.Pass through
Carbon is mixed to low-dielectric constant layer 30, the etch rate of low dielectric constant layer can be further adjusted, make both etchings
Speed is consistent, so as to avoid the side wall of groove 70 from being recessed.
Step S03：UV treatment or heating are carried out to the low-dielectric constant layer 30, to remove the pore-foaming agent
40 (as shown in Figure 9).
Specifically, in the present embodiment, ultraviolet irradiation or heating can decompose organic matter, then with gas
Form departs from film, forms hole, while ultraviolet can also link the silicon-carbon bonds in film again, forms finer and close skeleton
Structure, so supports hole.The time of UV treatment is preferably that between 20s-500s, treatment temperature is 300 degree -480 and spent
Between.
Step S04：The surface of low-dielectric constant layer 30 after treatment sequentially forms dielectric barrier layer 20 and metal hard
Mask layer 60 (as shown in Figure 10).
Wherein, low-dielectric constant layer 30 is preferably the porous silica layer of doped carbon, the material of metal hard mask layer 60
It can be, but not limited to Ta or Ti or W or TaN or TiN or WN.
Step S05：Using etching technics in the metal hard mask layer 60, dielectric barrier layer 20, carbon containing oxide layer 50
With formation groove 70 (as shown in figure 11) in the formed layer stack structure of low-dielectric constant layer 30.
Specifically, in the present embodiment, etching technics is preferably wet-etching technology, using wet-etching technology etching groove
When 70, it is preferred to use diluted hydrofluoric acid (Dilute Hydrofluoric Acid, DHF) solution etches groove 70.Wet etching work
The parameters such as temperature, the time of skill can require to set according to actual process, to DHF concentration and the parameter of time in existing method
It is required that stricter.DHF concentration preferably uses low concentration, can also use high concentration, can accelerate to remove oxidation using the DHF of high concentration
The efficiency of layer, DHF concentration typically selects 200: 1, and the concentration proportion of the DHF is deionized water and the body of 49% hydrofluoric acid
Product ratio.
After completing the procedure, other techniques in the Tong Hou roads to form cmos device, these techniques step can be continued executing with
Suddenly it can be formed using method familiar to those skilled in the art, therefore not to repeat here.
In summary, in the method for the reduction side wall damage of ultralow dielectric constant film that the present invention is provided, it is passed through carbon containing gas
Body carries out corona treatment to the low-k layer surface, and the carbon of incorporation makes carbon containing oxide layer in chemical solution
Etch rate close to the etch rate of low-dielectric constant layer, so as to avoid the side wall of groove structure from concave curved pattern occur, make quarter
Trenched side-wall after erosion keeps planarization, in addition, incorporation carbon can also reduce the dielectric constant values of the normal film of low dielectric, this
The method that invention is provided is easily achieved, and the treatment effect of low-dielectric constant layer is more notable, improves the electric property of device.
Only the preferred embodiments of the present invention above, embodiment is simultaneously not used to the scope of patent protection of the limitation present invention,
Therefore the equivalent structure change that every specification and accompanying drawing content with the present invention is made, similarly should be included in the present invention's
In protection domain.
Claims (10)
1. a kind of method for reducing side wall damage of ultralow dielectric constant film, it is characterised in that including：
Step S01：Dielectric barrier layer and low-dielectric constant layer are sequentially depositing on a semiconductor substrate, wherein, the low dielectric
Constant sheaf contains pore-foaming agent；
Step S02：It is passed through carbonaceous gas and corona treatment is carried out to the low-k layer surface, removes low Jie
The reactant on permittivity layers surface, and form carbon containing oxide layer in the low-k layer surface；The carbon of incorporation makes to contain
Oxidation of coal etch rate of the layer in chemical solution and reduces Jie of carbon containing oxide layer close to the etch rate of low-dielectric constant layer
Permittivity values；
Step S03：UV treatment or heating are carried out to the low-dielectric constant layer, to remove the pore-foaming agent；
Step S04：Low-k layer surface after treatment sequentially forms dielectric barrier layer and metal hard mask layer；
Step S05：It is normal in the metal hard mask layer, dielectric barrier layer, carbon containing oxide layer and low dielectric using etching technics
Groove is formed in several layers of the formed layer stack structure.
2. the method for side wall damage of ultralow dielectric constant film is reduced as claimed in claim 1, it is characterised in that described carbon containing
Gas is O2With CO2Mixed gas or pure CO2Gas.
3. the method for side wall damage of ultralow dielectric constant film is reduced as claimed in claim 2, it is characterised in that described carbon containing
Pressure needed for low-dielectric constant layer described in gas treatment is 2~10 supports, and power is 300~1500W, gas flow is 100~
2000sccm, processing time is 2s~20s.
4. the method for side wall damage of ultralow dielectric constant film is reduced as claimed in claim 1, it is characterised in that described carbon containing
Gas also includes inert gas.
5. the method for side wall damage of ultralow dielectric constant film is reduced as claimed in claim 4, it is characterised in that the inertia
Gas is helium, argon gas, nitrogen, nitrogen fluoride or carbon tetrafluoride one or more of combination therein.
6. the method for side wall damage of ultralow dielectric constant film is reduced as claimed in claim 1, it is characterised in that to described low
Dielectric constant layer mixes carbon.
7. the method for side wall damage of ultralow dielectric constant film is reduced as claimed in claim 6, it is characterised in that incorporation carbon member
The method of element is ion implanting or plasma doping.
8. the method for side wall damage of ultralow dielectric constant film is reduced as claimed in claim 1, it is characterised in that low Jie
Permittivity layers using plasma chemical vapor deposition or spin coating-gel method are formed, and the dielectric of the low-dielectric constant layer is normal
Number is 2.2-2.8.
9. the method for side wall damage of ultralow dielectric constant film is reduced as claimed in claim 1, it is characterised in that the metal
The material of hard mask layer is Ta or Ti or W or TaN or TiN or WN.
10. the method for side wall damage of ultralow dielectric constant film is reduced as claimed in claim 1, it is characterised in that the step
The material of dielectric barrier layer in rapid S01 is SiN or SiCN.
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| CN104569009A (en) * | 2014-12-29 | 2015-04-29 | 云南电网公司电力科学研究院 | Method for measuring X-ray radiation damage of solid insulating material based on microstructure and electric performance |
| CN116798952B (en) * | 2023-08-21 | 2023-11-14 | 合肥晶合集成电路股份有限公司 | Method for manufacturing semiconductor device and semiconductor device |
| CN117253850B (en) * | 2023-11-15 | 2024-02-02 | 合肥晶合集成电路股份有限公司 | Method for forming interconnection opening and method for forming interconnection structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903667A (en) * | 2011-07-26 | 2013-01-30 | 中芯国际集成电路制造(上海)有限公司 | Method for forming semiconductor device |
| CN103646914A (en) * | 2013-11-26 | 2014-03-19 | 上海华力微电子有限公司 | Ultraviolet treatment method of low-dielectric constant film |
| CN103871963A (en) * | 2014-02-21 | 2014-06-18 | 上海华力微电子有限公司 | Filming method of low-dielectric-constant film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903667A (en) * | 2011-07-26 | 2013-01-30 | 中芯国际集成电路制造(上海)有限公司 | Method for forming semiconductor device |
| CN103646914A (en) * | 2013-11-26 | 2014-03-19 | 上海华力微电子有限公司 | Ultraviolet treatment method of low-dielectric constant film |
| CN103871963A (en) * | 2014-02-21 | 2014-06-18 | 上海华力微电子有限公司 | Filming method of low-dielectric-constant film |
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